Polymerizable compound and use thereof

ABSTRACT

The present invention is to provide a polymerizable compound which can be a raw material for a resin having high transparency, good heat resistance and mechanical strength required for optical components such as plastic lenses and the like, while attaining a high refractive index (nd) exceeding 1.7, and an optical component composed of such a resin. 
     Disclosed is a compound represented by the general formula (3), 
     
       
         
         
             
             
         
       
     
     wherein, in the formula, M represents a metal atom; X 1  and X 2  each independently represent a sulfur atom or an oxygen atom; R 1  represents a divalent organic group; m represents an integer of 0 or 1 or more; p represents an integer of from 1 to n; q represents an integer of from 1 to (n−p); n represents a valence of a metal atom M; Yq each independently represent an inorganic or organic residue; and when q is 2 or more, Yq may be bonded to one another for forming a ring structure with the intermediary of a metal atom M.

This application is a Continuation Application of U.S. patentapplication Ser. No. 10/594,497 filed on Sep. 28, 2006, which is aNational Stage Application of PCT/JP2005/06399, filed on Mar. 31, 2005,the entire contents of which is incorporated by reference herein, andclaims priority to Japanese Patent Application Nos. 2004-106189, filedon Mar. 31, 2004, and 2004-240592, filed on Aug. 20, 2004, the entirecontents of each is incorporated by reference herein.

TECHNICAL FIELD

The present invention relates to a polymerizable compound comprising athietane group and a metal atom in a molecule, while attaining a veryhigh refractive index, which is useful as a raw material monomer for atransparent resin. Furthermore, the invention relates to a polymerizablecomposition comprising the compound, a resin obtained by polymerizationof the polymerizable composition and an optical component composed ofthe resin.

BACKGROUND ART

Since an inorganic glass has excellent general properties such asexcellent transparency and low optical anisotropy, the inorganic glasshas been widely used in many fields as a transparent material. However,the inorganic glass has drawbacks such that it is heavy and easilybroken, and has bad productivity when producing a product by molding andprocessing. As a result, a transparent organic polymer material (opticalresin) has been used as a material in place of the inorganic glass. Asthe optical component obtained from such an optical resin, there areexemplified, for example, a plastic lens such as a spectacle lens forvision correction or a camera lens of a digital camera and the like. Theoptical components have been put to practical use and have come intouse. In particular, for the purpose of use in a spectacle lens forvision correction, the plastic lens is lightweight and hardly broken,and can be tinted for granting great fashionability, as compared to thelens made of an inorganic glass. Making good use of such merits, theplastic lens has been widely used.

In the past, a crosslinking type resin obtained by castingpolymerization of diethylene glycol bisallylcarbonate (hereinafterreferred to as DAC) as an optical resin used for a spectacle lens underheating has been put to practical use. It has merits such thattransparency and heat resistance are excellent, and the chromaticaberration is low (Abbe number is high). Due to such merits, it has beenused the most for a general-purpose plastic spectacle lens for visioncorrection. However, there are problems such that wearing comfort andfashionability are worsened and the like since the central or edgethickness of the plastic lens becomes large because of the lowrefractive index (nd=1.50). Therefore, a resin for a plastic lens with ahigh refractive index capable of solving these problems has beendemanded and developed accordingly.

During such a trend, since polythiourethane containing a sulfur atomobtained by casting polymerization of a diisocyanate compound with apolythiol compound is excellent in its transparency and impactresistance, while attaining a high refractive index (nd=1.6 to 1.7), andhaving relatively high abbe number and the like. By achieving suchhighly superior characteristics, polythiourethane has been used for thepurpose of a high-quality plastic spectacle lens for vision correctionin which the thickness is thin and its weight is light.

On the other hand, in a trend to pursue an optical resin having a muchhigher refractive index, there have been proposed several resins such asa transparent resin obtained by polymerization of a compound having anepisulfide group in Patent Documents 1 and 2, a resin obtained bypolymerization of a metal-containing compound such as Se in PatentDocuments 3 and 4 or the like. However, the transparent resin obtainedby polymerization of a compound having an episulfide group has a problemin mechanical properties, while the resin obtained by polymerization ofa Se-containing metal compound has a problem in safety. Therefore, theyhave been demanded for further improvement. In recent years, there hasbeen demanded an optical resin having required general properties(transparency, thermal properties, mechanical properties and the like)as a plastic lens, while attaining a much higher refractive index (nd)exceeding 1.7. The development of such an optical resin has been made.

[Patent Document 1] Japanese Patent Laid-Open No. 1997-110979 [PatentDocument 2] Japanese Patent Laid-Open No. 1999-322930 [Patent Document3] Japanese Patent Laid-Open No. 1999-140046 [Patent Document 4]Japanese Patent Laid-Open No. 2001-296402 DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a polymerizablecompound, which has general properties (transparency, thermalproperties, mechanical properties and the like) required for opticalcomponents such as plastic lenses, while attaining a very highrefractive index (nd) exceeding 1.7, a resin obtained by polymerizationof the compound, and an optical component composed of the resin.

In order to solve the above problems, the present inventors haveconducted an extensive study and, as a result, the present invention hasbeen completed.

That is, the following matters specify the present invention.

[1] a compound comprising one or two or more thietane groups and a metalatom in a molecule;[2] a compound comprising one or two or more thietane groups representedby the general formulae (1) and/or (2), and a metal atom,

wherein, in the formula, A₁ to A₁₀ each independently represent ahydrogen atom or a monovalent inorganic or organic residue;

[3] a compound having one or two or more thietane groups in a molecule,and comprising a metal atom selected from an Sn atom, an Si atom, a Zratom, a Ge atom, a Ti atom, a Zn atom, an Al atom, a Fe atom, a Cu atom,a Pt atom, a Pb atom, an Au atom or an Ag atom;[4] a compound represented by the general formula (3),

wherein, in the formula, M represents a metal atom; X₁ and X₂ eachindependently represent a sulfur atom or an oxygen atom; R₁ represents adivalent organic group; m represents an integer of 0 or 1 or more; prepresents an integer of from 1 to n; q represents an integer of from 1to (n−p); n represents a valence of a metal atom M; Yq eachindependently represent an inorganic or organic residue; and when q is 2or more, Yq may be bonded to one another for forming a ring structurewith the intermediary of a metal atom M;

[5] a polymerizable composition comprising the aforementioned compound;[6] a resin obtained by polymerization of the aforementionedpolymerizable composition; and[7] an optical component composed of the aforementioned resin.

The resin obtained by polymerization of the polymerizable compound ofthe present invention has high transparency, good heat resistance andmechanical strength, while attaining a high refractive index (nd)exceeding 1.7. Therefore, the resin of the present invention is usefulas a resin used in an optical component such as a plastic lenses or thelike.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in more detail below.

The present invention relates to a compound having one or two or morethietane groups in a molecule and comprising a metal atom.

Examples of the metal atom used in the compound of the present inventionpreferably include an Sn atom, an Si atom, a Zr atom, a Ge atom, a Tiatom, a Zn atom, an Al atom, a Fe atom, a Cu atom, a Pt atom, a Pb atom,an Au atom or an Ag atom, more preferably an Sn atom, an Si atom, a Zratom, a Ti atom, a Ge atom, an Al atom, a Pb atom or a Zn atom, andfurther preferably an Sn atom, an Si atom, a Zr atom, a Ti atom or a Geatom.

Preferable examples of the thietane group contained in the compound ofthe present invention are thietane groups represented by the generalformula (1) or (2),

wherein, in the formula, A₁ to A₁₀ each independently represent ahydrogen atom, or a monovalent inorganic or organic residue.

A₁ to A₁₀ in the general formula (1) or (2) each independently representa hydrogen atom, or a monovalent inorganic or organic residue.

Examples of the monovalent inorganic or organic residue include ahalogen atom, a hydroxyl group, a thiol group, a substituted orunsubstituted alkyl group, a substituted or unsubstituted aryl group, asubstituted or unsubstituted aralkyl group, a substituted orunsubstituted alkoxy group, a substituted or unsubstituted alkylthiogroup, a substituted or unsubstituted aryloxy group, and a substitutedor unsubstituted arylthio group.

Concrete examples of the halogen atom include a fluorine atom, achlorine atom, a bromine atom, and an iodine atom.

Concrete examples of the substituted or unsubstituted alkyl groupinclude a linear alkyl group having 1 to 10 carbon atoms in total suchas a methyl group, an ethyl group, an n-propyl group, an n-butyl group,an n-pentyl group, an n-hexyl group and the like;

a branched alkyl group having 3 to 10 carbon atoms in total such as anisopropyl group, an isobutyl group, a sec-butyl group, an isopentylgroup, a sec-pentyl group, a 1-methylpentyl group, a 2-methylpentylgroup, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutylgroup, a 2-ethylbutyl group, a 1-methylhexyl group, a 2-methylhexylgroup, a 3-methylhexyl group, a 4-methylhexyl group, a 5-methylhexylgroup, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentylgroup, a 1-n-propylbutyl group, a 1-iso-propylbutyl group, a1-iso-propyl-2-methylpropyl group, a 1-methylheptyl group, a2-methylheptyl group, a 3-methylheptyl group, a 4-methylheptyl group, a5-methylheptyl group, a 6-methylheptyl group, a 1-ethylhexyl group, a2-ethylhexyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a1-n-propylpentyl group, a 2-n-propylpentyl group, a 1-iso-propylpentylgroup, a 2-iso-propylpentyl group, a 1-n-butylbutyl group, a1-iso-butylbutyl group, a 1-sec-butylbutyl group, a 1-tert-butylbutylgroup, a 2-tert-butylbutyl group, a tert-butyl group, a tert-pentylgroup, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a1,3-dimethylbutyl group, a 2,3-dimethylbutyl group, a1-ethyl-2-methylpropyl group, a 1,1-dimethylpentyl group, a1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a1,4-dimethylpentyl group, a 2,2-dimethylpentyl group, a2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a3,3-dimethylpentyl group, a 3,4-dimethylpentyl group, a1-ethyl-1-methylbutyl group, a 1-ethyl-2-methylbutyl group, a1-ethyl-3-methylbutyl group, a 2-ethyl-1-methylbutyl group, a2-ethyl-3-methylbutyl group, a 1,1-dimethylhexyl group, a1,2-dimethylhexyl group, a 1,3-dimethylhexyl group, a 1,4-dimethylhexylgroup, a 1,5-dimethylhexyl group, a 2,2-dimethylhexyl group, a2,3-dimethylhexyl group, a 2,4-dimethylhexyl group, a 2,5-dimethylhexylgroup, a 3,3-dimethylhexyl group, a 3,4-dimethylhexyl group, a3,5-dimethylhexyl group, a 4,4-dimethylhexyl group, a 4,5-dimethylhexylgroup, a 1-ethyl-2-methylpentyl group, a 1-ethyl-3-methylpentyl group, a1-ethyl-4-methylpentyl group, a 2-ethyl-1-methylpentyl group, a2-ethyl-2-methylpentyl group, a 2-ethyl-3-methylpentyl group, a2-ethyl-4-methylpentyl group, a 3-ethyl-1-methylpentyl group, a3-ethyl-2-methylpentyl group, a 3-ethyl-3-methylpentyl group, a3-ethyl-4-methylpentyl group, a 1-n-propyl-1-methylbutyl group, a1-n-propyl-2-methylbutyl group, a 1-n-propyl-3-methylbutyl group, a1-iso-propyl-1-methylbutyl group, a 1-iso-propyl-2-methylbutyl group, a1-iso-propyl-3-methylbutyl group, a 1,1-diethylbutyl group, a1,2-diethylbutyl group, a 1,1,2-trimethylpropyl group, a1,2,2-trimethylpropyl group, a 1,1,2-trimethylbutyl group, a1,1,3-trimethylbutyl group, a 1,2,3-trimethylbutyl group, a1,2,2-trimethylbutyl group, a 1,3,3-trimethylbutyl group, a2,3,3-trimethylbutyl group, a 1,1,2-trimethylpentyl group, a1,1,3-trimethylpentyl group, a 1,1,4-trimethylpentyl group, a1,2,2-trimethylpentyl group, a 1,2,3-trimethylpentyl group, a1,2,4-trimethylpentyl group, a 1,3,4-trimethylpentyl group, a2,2,3-trimethylpentyl group, a 2,2,4-trimethylpentyl group, a2,3,4-trimethylpentyl group, a 1,3,3-trimethylpentyl group, a2,3,3-trimethylpentyl group, a 3,3,4-trimethylpentyl group, a1,4,4-trimethylpentyl group, a 2,4,4-trimethylpentyl group, a3,4,4-trimethylpentyl group, a 1-ethyl-1,2-dimethylbutyl group, a1-ethyl-1,3-dimethylbutyl group, a 1-ethyl-2,3-dimethylbutyl group, a2-ethyl-1,1-dimethylbutyl group, a 2-ethyl-1,2-dimethylbutyl group, a2-ethyl-1,3-dimethylbutyl group, a 2-ethyl-2,3-dimethylbutyl group andthe like; anda saturated cyclic alkyl group having 5 to 10 carbon atoms in total suchas a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, amethoxycyclopentyl group, a methoxycyclohexyl group, a methylcyclohexylgroup, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a1,4-dimethylcyclohexyl group, an ethylcyclohexyl group and the like.

Concrete examples of the substituted or unsubstituted aryl group includearomatic hydrocarbons having not more than 20 carbon atoms in total suchas a phenyl group, a naphthyl group, an anthranyl group, acyclopentadienyl group and the like;

an alkyl-substituted aryl group having not more than 20 carbon atoms intotal such as a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 2-ethylphenyl group, a propylphenyl group, abutylphenyl group, a hexylphenyl group, a cyclohexylphenyl group, anoctylphenyl group, a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthylgroup, a 4-methyl-1-naphthyl group, a 5-methyl-1-naphthyl group, a6-methyl-1-naphthyl group, a 7-methyl-1-naphthyl group, a8-methyl-1-naphthyl group, a 1-methyl-2-naphthyl group, a3-methyl-2-naphthyl group, a 4-methyl-2-naphthyl group, a5-methyl-2-naphthyl group, a 6-methyl-2-naphthyl group, a7-methyl-2-naphthyl group, a 8-methyl-2-naphthyl group, a2-ethyl-1-naphthyl group, a 2,3-dimethylphenyl group, a2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a3,5-dimethylphenyl group, a 3,6-dimethylphenyl group, a2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group and the like;a monoalkoxyaryl group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group,a propoxyphenyl group, a butoxyphenyl group, a hexyloxyphenyl group, acyclohexyloxyphenyl group, an octyloxyphenyl group, a2-methoxy-1-naphthyl group, a 3-methoxy-1-naphthyl group, a4-methoxy-1-naphthyl group, a 5-methoxy-1-naphthyl group, a6-methoxy-1-naphthyl group, a 7-methoxy-1-naphthyl group, a8-methoxy-1-naphthyl group, a 1-methoxy-2-naphthyl group, a3-methoxy-2-naphthyl group, a 4-methoxy-2-naphthyl group, a5-methoxy-2-naphthyl group, a 6-methoxy-2-naphthyl group, a7-methoxy-2-naphthyl group, a 8-methoxy-2-naphthyl group, a2-ethoxy-1-naphthyl group and the like;a dialkoxyaryl group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2,3-dimethoxyphenylgroup, a 2,4-dimethoxyphenyl group, a 2,5-dimethoxyphenyl group, a2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,6-dimethoxyphenyl group, a4,5-dimethoxy-1-naphthyl group, a 4,7-dimethoxy-1-naphthyl group, a4,8-dimethoxy-1-naphthyl group, a 5,8-dimethoxy-1-naphthyl group, a5,8-dimethoxy-2-naphthyl group and the like;a trialkoxyaryl group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having nor morethan 10 carbon atoms is substituted, such as a 2,3,4-trimethoxyphenylgroup, a 2,3,5-trimethoxyphenyl group, a 2,3,6-trimethoxyphenyl group, a2,4,5-trimethoxyphenyl group, a 2,4,6-trimethoxyphenyl group, a3,4,5-trimethoxyphenyl group and the like; and an aryl group having notmore than 20 carbon atoms in total wherein a halogen atom issubstituted, such as a chlorophenyl group, a dichlorophenyl group, atrichlorophenyl group, a bromophenyl group, a dibromophenyl group, aniodophenyl group, a fluorophenyl group, a chloronaphthyl group, abromonaphthyl group, a difluorophenyl group, a trifluorophenyl group, atetrafluorophenyl group, a pentafluorophenyl group and the like.

Concrete examples of the substituted or unsubstituted aralkyl groupinclude a benzyl group, a phenethyl group, a phenylpropyl group, anaphthylethyl group, or a methyl group, an ethyl group and a propylgroup having an aryl group specifically mentioned as examples of thesubstituted or unsubstituted aryl group beforehand in a side chain.

Concrete examples of the substituted or unsubstituted alkyloxy groupinclude a linear or branched alkoxy group having 1 to 10 carbon atoms intotal such as a methoxy group, an ethoxy group, an n-propoxy group, aniso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxygroup, an n-pentyloxy group, an iso-pentyloxy group, an n-hexyloxygroup, an iso-hexyloxy group, a 2-ethylhexyloxy group, a3,5,5-trimethylhexyloxy group, an n-heptyloxy group, an n-octyloxygroup, an n-nonyloxy group and the like;

a cycloalkoxy group having 5 to 10 carbon atoms in total such as acyclopentyloxy group, a cyclohexyloxy group and the like;an alkoxyalkoxy group having 1 to 10 carbon atoms in total such as amethoxymethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, ann-propoxymethoxy group, an iso-propoxymethoxy group, an n-propoxyethoxygroup, an iso-propoxyethoxy group, an n-butoxyethoxy group, aniso-butoxyethoxy group, a tert-butoxyethoxy group, an n-pentyloxyethoxygroup, an iso-pentyloxyethoxy group, an n-hexyloxyethoxy group, aniso-hexyloxyethoxy group, an n-heptyloxyethoxy group and the like; andan aralkyloxy group such as a benzyloxy group.

Concrete examples of the substituted or unsubstituted alkylthio groupinclude a linear or branched alkylthio group having 1 to 10 carbon atomsin total such as a methylthio group, an ethylthio group, an n-propylthiogroup, an i-propylthio group, an n-butylthio group, an i-butylthiogroup, a sec-butylthio group, a t-butylthio group, an n-pentylthiogroup, an iso-pentylthio group, an n-hexylthio group, an iso-hexylthiogroup, a 2-ethylhexylthio group, a 3,5,5-trimethylhexylthio group, ann-heptylthio group, an n-octylthio group, an n-nonylthio group and thelike;

a cycloalkylthio group having 5 to 10 carbon atoms in total such as acyclopentylthio group, a cyclohexylthio group and the like;an alkoxyalkylthio group having 1 to 10 carbon atoms in total such as amethoxyethylthio group, an ethoxyethylthio group, an n-propoxyethylthiogroup, an iso-propoxyethylthio group, an n-butoxyethylthio group, aniso-butoxyethylthio group, a tert-butoxyethylthio group, ann-pentyloxyethylthio group, an iso-pentyloxyethylthio group, ann-hexyloxyethylthio group, an iso-hexyloxyethylthio group, ann-heptyloxyethylthio group and the like;an aralkylthio group such as a benzylthio group and the like; andan alkylthioalkylthio group having 1 to 10 carbon atoms in total such asa methylthioethylthio group, an ethylthioethylthio group, ann-propylthioethylthio group, an iso-propylthioethylthio group, ann-butylthioethylthio group, an iso-butylthioethylthio group, atert-butylthioethylthio group, an n-pentylthioethylthio group, aniso-pentylthioethylthio group, an n-hexylthioethylthio group, aniso-hexylthioethylthio group, an n-heptylthioethylthio group and thelike.

Concrete examples of the substituted or unsubstituted aryloxy groupinclude an unsubstituted or alkyl-substituted aryloxy group having notmore than 20 carbon atoms in total such as a phenyloxy group, anaphthyloxy group, an anthranyloxy group, a 2-methylphenyloxy group, a3-methylphenyloxy group, a 4-methylphenyloxy group, a 2-ethylphenyloxygroup, a propylphenyloxy group, a butylphenyloxy group, a hexylphenyloxygroup, a cyclohexylphenyloxy group, an octylphenyloxy group, a2-methyl-1-naphthyloxy group, a 3-methyl-1-naphthyloxy group, a4-methyl-1-naphthyloxy group, a 5-methyl-1-naphthyloxy group, a6-methyl-1-naphthyloxy group, a 7-methyl-1-naphthyloxy group, a8-methyl-1-naphthyloxy group, a 1-methyl-2-naphthyloxy group, a3-methyl-2-naphthyloxy group, a 4-methyl-2-naphthyloxy group, a5-methyl-2-naphthyloxy group, a 6-methyl-2-naphthyloxy group, a7-methyl-2-naphthyloxy group, a 8-methyl-2-naphthyloxy group, a2-ethyl-1-naphthyloxy group, a 2,3-dimethylphenyloxy group, a2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a3,5-dimethylphenyloxy group, a 3,6-dimethylphenyloxy group, a2,3,4-trimethylphenyloxy group, a 2,3,5-trimethylphenyloxy group, a2,3,6-trimethylphenyloxy group, a 2,4,5-trimethylphenyloxy group, a2,4,6-trimethylphenyloxy group, a 3,4,5-trimethylphenyloxy group and thelike;

a monoalkoxyaryloxy group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2-methoxyphenyloxy group,a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a2-ethoxyphenyloxy group, a propoxyphenyloxy group, a butoxyphenyloxygroup, a hexyloxyphenyloxy group, a cyclohexyloxyphenyloxy group, anoctyloxyphenyloxy group, a 2-methoxy-1-naphthyloxy group, a3-methoxy-1-naphthyloxy group, a 4-methoxy-1-naphthyloxy group, a5-methoxy-1-naphthyloxy group, a 6-methoxy-1-naphthyloxy group, a7-methoxy-1-naphthyloxy group, a 8-methoxy-1-naphthyloxy group, a1-methoxy-2-naphthyloxy group, a 3-methoxy-2-naphthyloxy group, a4-methoxy-2-naphthyloxy group, a 5-methoxy-2-naphthyloxy group, a6-methoxy-2-naphthyloxy group, a 7-methoxy-2-naphthyloxy group, a8-methoxy-2-naphthyloxy group, a 2-ethoxy-1-naphthyloxy group and thelike;a dialkoxyaryloxy group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2,3-dimethoxyphenyloxygroup, a 2,4-dimethoxyphenyloxy group, a 2,5-dimethoxyphenyloxy group, a2,6-dimethoxyphenyloxy group, a 3,4-dimethoxyphenyloxy group, a3,5-dimethoxyphenyloxy group, a 3,6-dimethoxyphenyloxy group, a4,5-dimethoxy-1-naphthyloxy group, a 4,7-dimethoxy-1-naphthyloxy group,a 4,8-dimethoxy-1-naphthyloxy group, a 5,8-dimethoxy-1-naphthyloxygroup, a 5,8-dimethoxy-2-naphthyloxy group and the like;a trialkoxyaryloxy group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2,3,4-trimethoxyphenyloxygroup, a 2,3,5-trimethoxyphenyloxy group, a 2,3,6-trimethoxyphenyloxygroup, a 2,4,5-trimethoxyphenyloxy group, a 2,4,6-trimethoxyphenyloxygroup, a 3,4,5-trimethoxyphenyloxy group and the like; andan aryloxy group having not more than 20 carbon atoms in total wherein ahalogen atom is substituted, such as a chlorophenyloxy group, adichlorophenyloxy group, a trichlorophenyloxy group, a bromophenyloxygroup, a dibromophenyloxy group, an iodophenyloxy group, afluorophenyloxy group, a chloronaphthyloxy group, a bromonaphthyloxygroup, a difluorophenyloxy group, a trifluorophenyloxy group, atetrafluorophenyloxy group, a pentafluorophenyloxy group and the like.

Concrete examples of the substituted or unsubstituted arylthio groupinclude an unsubstituted or alkyl-substituted arylthio group having notmore than 20 carbon atoms in total such as a phenylthio group, anaphthylthio group, an anthranylthio group, a 2-methylphenylthio group,a 3-methylphenylthio group, a 4-methylphenylthio group, a2-ethylphenylthio group, a propylphenylthio group, a butylphenylthiogroup, a hexylphenylthio group, a cyclohexylphenylthio group, anoctylphenylthio group, a 2-methyl-1-naphthylthio group, a3-methyl-1-naphthylthio group, a 4-methyl-1-naphthylthio group, a5-methyl-1-naphthylthio group, a 6-methyl-1-naphthylthio group, a7-methyl-1-naphthylthio group, a 8-methyl-1-naphthylthio group, a1-methyl-2-naphthylthio group, a 3-methyl-2-naphthylthio group, a4-methyl-2-naphthylthio group, a 5-methyl-2-naphthylthio group, a6-methyl-2-naphthylthio group, a 7-methyl-2-naphthylthio group, a8-methyl-2-naphthylthio group, a 2-ethyl-1-naphthylthio group, a2,3-dimethylphenylthio group, a 2,4-dimethylphenylthio group, a2,5-dimethylphenylthio group, a 2,6-dimethylphenylthio group, a3,4-dimethylphenylthio group, a 3,5-dimethylphenylthio group, a3,6-dimethylphenylthio group, a 2,3,4-trimethylphenylthio group, a2,3,5-trimethylphenylthio group, a 2,3,6-trimethylphenylthio group, a2,4,5-trimethylphenylthio group, a 2,4,6-trimethylphenylthio group, a3,4,5-trimethylphenylthio group and the like;

a monoalkoxyarylthio group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2-methoxyphenylthiogroup, a 3-methoxyphenylthio group, a 4-methoxyphenylthio group, a2-ethoxyphenylthio group, a propoxyphenylthio group, a butoxyphenylthiogroup, a hexyloxyphenylthio group, a cyclohexyloxyphenylthio group, anoctyloxyphenylthio group, a 2-methoxy-1-naphthylthio group, a3-methoxy-1-naphthylthio group, a 4-methoxy-1-naphthylthio group, a5-methoxy-1-naphthylthio group, a 6-methoxy-1-naphthylthio group, a7-methoxy-1-naphthylthio group, a 8-methoxy-1-naphthylthio group, a1-methoxy-2-naphthylthio group, a 3-methoxy-2-naphthylthio group, a4-methoxy-2-naphthylthio group, a 5-methoxy-2-naphthylthio group, a6-methoxy-2-naphthylthio group, a 7-methoxy-2-naphthylthio group, a8-methoxy-2-naphthylthio group, a 2-ethoxy-1-naphthylthio group and thelike;a dialkoxyarylthio group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a 2,3-dimethoxyphenylthiogroup, a 2,4-dimethoxyphenylthio group, a 2,5-dimethoxyphenylthio group,a 2,6-dimethoxyphenylthio group, a 3,4-dimethoxyphenylthio group, a3,5-dimethoxyphenylthio group, a 3,6-dimethoxyphenylthio group, a4,5-dimethoxy-1-naphthylthio group, a 4,7-dimethoxy-1-naphthylthiogroup, a 4,8-dimethoxy-1-naphthylthio group, a5,8-dimethoxy-1-naphthylthio group, a 5,8-dimethoxy-2-naphthylthio groupand the like;a trialkoxyarylthio group having not more than 20 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 10 carbon atoms is substituted, such as a2,3,4-trimethoxyphenylthio group, a 2,3,5-trimethoxyphenylthio group, a2,3,6-trimethoxyphenylthio group, a 2,4,5-trimethoxyphenylthio group, a2,4,6-trimethoxyphenylthio group, a 3,4,5-trimethoxyphenylthio group andthe like; andan arylthio group having not more than 20 carbon atoms in total whereina halogen atom is substituted, such as a chlorophenylthio group, adichlorophenylthio group, a trichlorophenylthio group, a bromophenylthiogroup, a dibromophenylthio group, an iodophenylthio group, afluorophenylthio group, a chloronaphthylthio group, a bromonaphthylthiogroup, a difluorophenylthio group, a trifluorophenylthio group, atetrafluorophenylthio group, a pentafluorophenylthio group and the like.However, the present invention is not restricted thereto.

A₁ to A₁₀ preferably represent a hydrogen atom. Preferable examples ofthe halogen atom include a chlorine atom, a bromine atom and an iodineatom.

Preferable examples of the substituted or unsubstituted alkyl groupinclude a linear alkyl group having 1 to 6 carbon atoms in total such asa methyl group, an ethyl group, an n-propyl group, an n-butyl group, ann-pentyl group, an n-hexyl group and the like;

a branched alkyl group having 3 to 6 carbon atoms in total such as anisopropyl group, an isobutyl group, a sec-butyl group, an isopentylgroup, a sec-pentyl group, a 1-methylpentyl group, a 2-methylpentylgroup, a 3-methylpentyl group, a 4-methylpentyl group, a 1-ethylbutylgroup, a 2-ethylbutyl group, a tert-butyl group, a tert-pentyl group, a1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutylgroup, a 2,3-dimethylbutyl group and the like; anda saturated cyclic alkyl group having 5 to 6 carbon atoms in total suchas a cyclopentyl group, a cyclohexyl group and the like.

Preferable examples of the substituted or unsubstituted aryl groupinclude aromatic hydrocarbons having not more than 12 carbon atoms intotal such as a phenyl group, a naphthyl group, a cyclopentadienyl groupand the like;

an alkyl-substituted aryl group having not more than 12 carbon atoms intotal such as a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 2-ethylphenyl group, a propylphenyl group, abutylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenylgroup, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a3,6-dimethylphenyl group, a 2,3,4-trimethylphenyl group, a2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a3,4,5-trimethylphenyl group and the like;a monoalkoxyaryl group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group,a propoxyphenyl group, a butoxyphenyl group and the like;a dialkoxyaryl group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2,3-dimethoxyphenyl group,a 2,4-dimethoxyphenyl group, a 2,5-dimethoxyphenyl group, a2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,6-dimethoxyphenyl group and the like; andan aryl group having not more than 12 carbon atoms in total wherein ahalogen atom is substituted, such as a chlorophenyl group, adichlorophenyl group, a trichlorophenyl group, a bromophenyl group, adibromophenyl group, an iodophenyl group, a fluorophenyl group, achloronaphthyl group, a bromonaphthyl group, a difluorophenyl group, atrifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenylgroup and the like.

Preferable examples of the substituted or unsubstituted aralkyl groupinclude an aralkyl group having not more than 12 carbon atoms in totalsuch as a benzyl group, a phenethyl group, a phenylpropyl group and thelike.

Preferable examples of the substituted or unsubstituted alkyloxy groupinclude a linear or branched alkoxy group having 1 to 6 carbon atoms intotal such as a methoxy group, an ethoxy group, an n-propoxy group, aniso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxygroup, an n-pentyloxy group, an iso-pentyloxy group, an n-hexyloxygroup, an iso-hexyloxy group and the like;

a cycloalkoxy group having 5 to 6 carbon atoms in total such as acyclopentyloxy group, a cyclohexyloxy group and the like; andan alkoxyalkoxy group having 1 to 6 carbon atoms in total such as amethoxymethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, ann-propoxymethoxy group, an iso-propoxymethoxy group, an n-propoxyethoxygroup, an iso-propoxyethoxy group, an n-butoxyethoxy group, aniso-butoxyethoxy group, a tert-butoxyethoxy group and the like.

Preferable examples of the substituted or unsubstituted alkylthio groupinclude a linear or branched alkylthio group having 1 to 6 carbon atomsin total such as a methylthio group, an ethylthio group, an n-propylthiogroup, an i-propylthio group, an n-butylthio group, an i-butylthiogroup, a sec-butylthio group, a t-butylthio group, an n-pentylthiogroup, an iso-pentylthio group, an n-hexylthio group, an iso-hexylthiogroup and the like;

a cycloalkylthio group having 5 to 6 carbon atoms in total such as acyclopentylthio group, a cyclohexylthio group and the like;an alkoxyalkylthio group having 1 to 6 carbon atoms in total such as amethoxyethylthio group, an ethoxyethylthio group, an n-propoxyethylthiogroup, an iso-propoxyethylthio group, an n-butoxyethylthio group, aniso-butoxyethylthio group, a tert-butoxyethylthio group and the like;andan alkylthioalkylthio group having 1 to 6 carbon atoms in total such asa methylthioethylthio group, an ethylthioethylthio group, ann-propylthioethylthio group, an iso-propylthioethylthio group, ann-butylthioethylthio group, an iso-butylthioethylthio group, atert-butylthioethylthio group and the like.

Preferable examples of the substituted or unsubstituted aryloxy groupinclude an unsubstituted or alkyl-substituted aryloxy group having notmore than 12 carbon atoms in total such as a phenyloxy group, anaphthyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group,a 4-methylphenyloxy group, a 2-ethylphenyloxy group, a propylphenyloxygroup, a butylphenyloxy group, a hexylphenyloxy group, acyclohexylphenyloxy group, a 2,4-dimethylphenyloxy group, a2,5-dimethylphenyloxy group, a 2,6-dimethylphenyloxy group, a3,4-dimethylphenyloxy group, a 3,5-dimethylphenyloxy group, a3,6-dimethylphenyloxy group, a 2,3,4-trimethylphenyloxy group, a2,3,5-trimethylphenyloxy group, a 2,3,6-trimethylphenyloxy group, a2,4,5-trimethylphenyloxy group, a 2,4,6-trimethylphenyloxy group, a3,4,5-trimethylphenyloxy group and the like;

a monoalkoxyaryloxy group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2-methoxyphenyloxy group,a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a2-ethoxyphenyloxy group, a propoxyphenyloxy group, a butoxyphenyloxygroup, a hexyloxyphenyloxy group, a cyclohexyloxyphenyloxy group and thelike;a dialkoxyaryloxy group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2,3-dimethoxyphenyloxygroup, a 2,4-dimethoxyphenyloxy group, a 2,5-dimethoxyphenyloxy group, a2,6-dimethoxyphenyloxy group, a 3,4-dimethoxyphenyloxy group, a3,5-dimethoxyphenyloxy group, a 3,6-dimethoxyphenyloxy group and thelike; andan aryloxy group having not more than 12 carbon atoms in total wherein ahalogen atom is substituted, such as a chlorophenyloxy group, adichlorophenyloxy group, a trichlorophenyloxy group, a bromophenyloxygroup, a dibromophenyloxy group, an iodophenyloxy group, afluorophenyloxy group, a chloronaphthyloxy group, a bromonaphthyloxygroup, a difluorophenyloxy group, a trifluorophenyloxy group, atetrafluorophenyloxy group, a pentafluorophenyloxy group and the like.

Preferable examples of the substituted or unsubstituted arylthio groupinclude an unsubstituted or alkyl-substituted arylthio group having notmore than 12 carbon atoms in total such as a phenylthio group, anaphthylthio group, a 2-methylphenylthio group, a 3-methylphenylthiogroup, a 4-methylphenylthio group, a 2-ethylphenylthio group, apropylphenylthio group, a butylphenylthio group, a hexylphenylthiogroup, a cyclohexylphenylthio group, a 2,4-dimethylphenylthio group, a2,5-dimethylphenylthio group, a 2,6-dimethylphenylthio group, a3,4-dimethylphenylthio group, a 3,5-dimethylphenylthio group, a3,6-dimethylphenylthio group, a 2,3,4-trimethylphenylthio group, a2,3,5-trimethylphenylthio group, a 2,3,6-trimethylphenylthio group, a2,4,5-trimethylphenylthio group, a 2,4,6-trimethylphenylthio group, a3,4,5-trimethylphenylthio group and the like;

a monoalkoxyarylthio group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2-methoxyphenylthio group,a 3-methoxyphenylthio group, a 4-methoxyphenylthio group, a2-ethoxyphenylthio group, a propoxyphenylthio group, a butoxyphenylthiogroup, a hexyloxyphenylthio group, a cyclohexyloxyphenylthio group andthe like;a dialkoxyarylthio group having not more than 12 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 6 carbon atoms is substituted, such as a 2,3-dimethoxyphenylthiogroup, a 2,4-dimethoxyphenylthio group, a 2,5-dimethoxyphenylthio group,a 2,6-dimethoxyphenylthio group, a 3,4-dimethoxyphenylthio group, a3,5-dimethoxyphenylthio group, a 3,6-dimethoxyphenylthio group, a4,5-dimethoxy-1-naphthylthio group, a 4,7-dimethoxy-1-naphthylthiogroup, a 4,8-dimethoxy-1-naphthylthio group, a5,8-dimethoxy-1-naphthylthio group, a 5,8-dimethoxy-2-naphthylthio groupand the like; andan arylthio group having not more than 12 carbon atoms in total whereina halogen atom is substituted, such as a chlorophenylthio group, adichlorophenylthio group, a trichlorophenylthio group, a bromophenylthiogroup, a dibromophenylthio group, an iodophenylthio group, afluorophenylthio group, a chloronaphthylthio group, a bromonaphthylthiogroup, a difluorophenylthio group, a trifluorophenylthio group, atetrafluorophenylthio group, a pentafluorophenylthio group and the like.

More preferable example includes a hydrogen atom. More preferableexamples of the halogen atom include a chlorine atom and a bromine atom.

More preferable examples of the substituted or unsubstituted alkyl groupinclude a linear or branched alkyl group having 1 to 3 carbon atoms intotal such as a methyl group, an ethyl group, an iso-propyl group andthe like.

More preferable examples of the substituted or unsubstituted aryl groupinclude aromatic hydrocarbons having not more than 12 carbon atoms intotal such as a phenyl group, a naphthyl group, a cyclopentadienyl groupand the like;

an alkyl-substituted aryl group having not more than 9 carbon atoms intotal such as a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 2-ethylphenyl group, a propylphenyl group, a2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a3,6-dimethylphenyl group and the like;a monoalkoxyaryl group having not more than 9 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 3 carbon atoms is substituted, such as a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group,a propoxyphenyl group and the like; andan aryl group having not more than 12 carbon atoms in total wherein ahalogen atom is substituted, such as a chlorophenyl group, adichlorophenyl group, a trichlorophenyl group, a bromophenyl group, adibromophenyl group, a chloronaphthyl group, a bromonaphthyl group andthe like.

More preferable examples of the substituted or unsubstituted aralkylgroup include an aralkyl group having not more than 9 carbon atoms intotal such as a benzyl group, a phenethyl group, a phenylpropyl groupand the like.

More preferable examples of the substituted or unsubstituted alkyloxygroup include a linear or branched alkoxy group having 1 to 3 carbonatoms in total such as a methoxy group, an ethoxy group, an iso-propoxygroup and the like; and

a cycloalkoxy group having 5 to 6 carbon atoms in total such as acyclopentyloxy group, a cyclohexyloxy group and the like.

More preferable examples of the substituted or unsubstituted alkylthiogroup include a linear or branched alkylthio group having 1 to 3 carbonatoms in total such as a methylthio group, an ethylthio group, ann-propylthio group, an i-propylthio group and the like;

a cycloalkylthio group having 5 to 6 carbon atoms in total such as acyclopentylthio group, a cyclohexylthio group and the like; andan alkylthioalkylthio group having 1 to 6 carbon atoms in total such asa methylthioethylthio group, an ethylthioethylthio group, ann-propylthioethylthio group, an iso-propylthioethylthio group, ann-butylthioethylthio group, an iso-butylthioethylthio group, atert-butylthioethylthio group and the like.

More preferable examples of the substituted or unsubstituted aryloxygroup include an unsubstituted or alkyl-substituted aryloxy group havingnot more than 9 carbon atoms in total such as a phenyloxy group, anaphthyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group,a 4-methylphenyloxy group, a 2-ethylphenyloxy group, a propylphenyloxygroup, a 2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a3,5-dimethylphenyloxy group, a 3,6-dimethylphenyloxy group and the like;

a monoalkoxyaryloxy group having not more than 9 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 3 carbon atoms is substituted, such as a 2-methoxyphenyloxy group,a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a2-ethoxyphenyloxy group, a propoxyphenyloxy group and the like; andan aryloxy group having not more than 12 carbon atoms in total wherein ahalogen atom is substituted, such as a chlorophenyloxy group, adichlorophenyloxy group, a trichlorophenyloxy group, a bromophenyloxygroup, a dibromophenyloxy group, a chloronaphthyloxy group, abromonaphthyloxy group and the like.

More preferable examples of the substituted or unsubstituted arylthiogroup include an unsubstitued or alkyl-substituted arylthio group havingnot more than 9 carbon atoms in total such as a phenylthio group, a2-methylphenylthio group, a 3-methylphenylthio group, a4-methylphenylthio group, a 2-ethylphenylthio group, a propylphenylthiogroup, a 2,4-dimethylphenylthio group, a 2,5-dimethylphenylthio group, a2,6-dimethylphenylthio group, a 3,4-dimethylphenylthio group, a3,5-dimethylphenylthio group, a 3,6-dimethylphenylthio group and thelike;

a monoalkoxyarylthio group having not more than 9 carbon atoms in totalwherein a substituted or unsubstituted alkyloxy group having not morethan 3 carbon atoms is substituted, such as a 2-methoxyphenylthio group,a 3-methoxyphenylthio group, a 4-methoxyphenylthio group, a2-ethoxyphenylthio group, a propoxyphenylthio group and the like; andan arylthio group having not more than 12 carbon atoms in total whereina halogen atom is substituted, such as a chlorophenylthio group, adichlorophenylthio group, a trichlorophenylthio group, a bromophenylthiogroup, a dibromophenylthio group, a chloronaphthylthio group, abromonaphthylthio group and the like.

The thietane group represented by the general formula (1) or (2) isspecifically exemplified in the following Tables 1 and 2. However, thethietane group is not restricted to the following.

TABLE 1 [Concrete examples of the thietane group represented by thegeneral formula (1)] Thietane Group Nos. A₁ A₂ A₃ A₄ A₅ 1-1 H H H H H1-2 Cl H H H H 1-3 H H H H Cl 1-4 CH₃ H H H H 1-5 H H H H CH₃ 1-6 C₂H₅ HH H H 1-7 H H H H C₂H₅ 1-8 C₆H₅ H H H H 1-9 H H H H C₆H₅ 1-10 CH₃S H H HH 1-11 H H H H CH₃S 1-12 C₆H₅S H H H H 1-13 H H H H C₆H₅S 1-14 CH₃O H HH H 1-15 H H H H CH₃O 1-16 C₆H₅O H H H H 1-17 H H H H C₆H₅O 1-18 C₆H₅CH₂H H H H 1-19 H H H H C₆H₅CH₂ 1-20 CH₃ CH₃ H H H 1-21 C₂H₅ C₂H₅ H H H1-22 C₆H₅ C₆H₅ H H H 1-23 CH₃S CH₃S H H H 1-24 C₆H₅S C₆H₅S H H H 1-25CH₃O CH₃O H H H 1-26 C₆H₅O C₆H₅O H H H 1-27 CH₃ H CH₃ H H 1-28 C₆H₅ HC₆H₅ H H 1-29 CH₃S H CH₃S H H 1-30 C₆H₅S H C₆H₅S H H 1-31 CH₃ H H H CH₃1-32 C₆H₅ H H H C₆H₅ 1-33 CH₃S H H H CH₃S 1-34 C₆H₅S H H H C₆H₅S 1-35CH₃O H H H CH₃O 1-36 C₆H₅O H H H C₆H₅O

TABLE 2 [Concrete examples of the thietane group represented by thegeneral formula (2)] Thietane Group Nos. A₆ A₇ A₈ A₉ A₁₀ 2-1 H H H H H2-2 Cl H H H H 2-3 H Cl H H H 2-4 H H H Cl H 2-5 CH₃ H H H H 2-6 H CH₃ HH H 2-7 H H H CH₃ H 2-8 C₆H₅ H H H H 2-9 H C₆H₅ H H H 2-10 H H H C₆H₅ H2-11 CH₃S H H H H 2-12 H CH₃S H H H 2-13 H H H CH₃S H 2-14 C₆H₅S H H H H2-15 H C₆H₅S H H H 2-16 H H H C₆H₅S H 2-17 CH₃O H H H H 2-18 H CH₃O H HH 2-19 H H H CH₃O H 2-20 C₆H₅O H H H H 2-21 H C₆H₅O H H H 2-22 H H HC₆H₅O H 2-23 C₆H₅CH₂ H H H H 2-24 H C₆H₅CH₂ H H H 2-25 H H H C₆H₅CH₂ H2-26 H CH₃ CH₃ H H 2-27 H C₆H₅ C₆H₅ H H 2-28 H CH₃S CH₃S H H 2-29 HC₆H₅S C₆H₅S H H 2-30 H CH₃O CH₃O H H 2-31 H C₆H₅O C₆H₅O H H 2-32 H H HCH₃ CH₃ 2-33 H H H C₆H₅ C₆H₅ 2-34 H H H CH₃S CH₃S 2-35 H H H C₆H₅S C₆H₅S2-36 H H H CH₃O CH₃O 2-37 H H H C₆H₅O C₆H₅O 2-38 CH₃ CH₃ H H H 2-39 CH₃H H CH₃ H 2-40 C₆H₅ C₆H₅ H H H 2-41 C₆H₅ H H C₆H₅ H 2-42 CH₃S CH₃S H H H2-43 CH₃S H H CH₃S H 2-44 C₆H₅S C₆H₅S H H H 2-45 C₆H₅S H H C₆H₅S H 2-46CH₃O CH₃O H H H 2-47 CH₃O H H CH₃O H 2-48 C₆H₅O C₆H₅O H H H 2-49 C₆H₅O HH C₆H₅O H 2-50 H CH₃ H CH₃ H 2-51 H C₆H₅ H C₆H₅ H 2-52 H CH₃S H CH₃S H2-53 H C₆H₅S H C₆H₅S H 2-54 H CH₃O H CH₃O H 2-55 H C₆H₅O H C₆H₅O H

Bonding of the thietane group represented by the general formula (1) or(2) to a metal atom in the present invention is not particularlylimited. That is, the thietane group may be directly bonded to a metalatom, or may be bonded to a metal group through an appropriate linkinggroup. Examples of the linking group include, though not restricted to,a chained or cyclic aliphatic group, an aromatic group, anaromatic-aliphatic group, or a group represented by the general formula(4),

wherein, in the formula, X₁, X₂, R₁ and m are the same as X₁, X₂, R₁ andm in the general formula (3). Concrete examples of the linking groupinclude the following.

Concrete examples of the chained or cyclic aliphatic group include asubstituted or unsubstituted chained or cyclic aliphatic group having 1to 20 carbon atoms such as a methylene group, an ethylene group, a1,2-dichloroethylene group, a trimethylene group, a tetramethylenegroup, a pentamethylene group, a cyclopentylene group, a hexamethylenegroup, a cyclohexylene group, a heptamethylene group, an octamethylenegroup, a nonamethylene group, a decamethylene group, an undecamethylenegroup, a dodecamethylene group, a tridecamethylene group, atetradecamethylene group, a pentadecamethylene group and the like.

Concrete examples of the aromatic group or aromatic-aliphatic groupinclude a substituted or unsubstituted aromatic group having 5 to 20carbon atoms such as a phenylene group, a chlorophenylene group, anaphthylene group, an indenylene group, an anthracenylene group, afluorenylene group and the like; and

a substituted or unsubstituted aromatic-aliphatic group having 6 to 20carbon atoms such as a —C₆H₄—CH₂— group, a —CH₂—C₆H₄—CH₂— group, a—CH₂—C₆H₃ (Cl)—CH₂— group, a —C₁₀H₆—CH₂— group, a —CH₂—C₁₀H₆—CH₂— group,a —CH₂CH₂—C₆H₄—CH₂CH₂— group and the like.Concrete examples of the group represented by the general formula (4)include those exemplified for X₁, X₂, R₁ and m in the general formula(3) to be described below and in combination thereof.

These linking groups may contain a heteroatom except for a carbon atomor a hydrogen atom in the group. Examples of the heteroatom include anoxygen atom or a sulfur atom. Considering the desired effect of thepresent invention, a sulfur atom is preferable.

The thietane group represented by the general formula (1) or (2) ispreferably directly bonded to a metal atom.

Preferable examples of the chained or cyclic aliphatic group include asubstituted or unsubstituted chained or cyclic aliphatic group having 1to 6 carbon atoms such as a methylene group, an ethylene group, a1,2-dichloroethylene group, a trimethylene group, a cyclopentylenegroup, a cyclohexylene group and the like.

Preferable examples of the aromatic group or aromatic-aliphatic groupinclude a substituted or unsubstituted aromatic group having 5 to 15carbon atoms such as a phenylene group, a chlorophenylene group, anaphthylene group, an indenylene group, an anthracenylene group, afluorenylene group and the like; and

a substituted or unsubstituted aromatic-aliphatic group having 6 to 15carbon atoms such as a —C₆H₄—CH₂— group, a —CH₂—C₆H₄—CH₂— group, a—CH₂—C₆H₃ (Cl)—CH₂— group, a —C₁₀H₆CH₂—group, a —CH₂—C₁₀H₆—CH₂— group, a—CH₂CH₂—C₆H₄—CH₂CH₂— group and the like.

Preferable examples of the group represented by the general formula (4)include those preferably exemplified for X₁, X₂, R₁ and m in the generalformula (3) to be described below and in combination thereof.

Furthermore, the present invention may contain the thietane grouprepresented by the general formula (1) or (2), and contain a pluralityof other thietane groups represented by the general formula (1) or (2)in the same molecule.

Preferred examples of the compound of the present invention includecompounds represented by the general formula (3),

wherein, in the formula, M represents a metal atom; X₁ and X₂ eachindependently represent a sulfur atom or an oxygen atom; R₁ represents adivalent organic group; m represents an integer of 0 or 1 or more; prepresents an integer of from 1 to n; q represents an integer of from 1to (n−p); n represents a valence of a metal atom M; Yq eachindependently represent an inorganic or organic residue; and when q is 2or more, Yq may be bonded to one another for forming a ring structurewith the intermediary of a metal atom M.

M in the general formula (3) represents a metal atom, preferably an Snatom, an Si atom, a Zr atom, a Ge atom, a Ti atom, a Zn atom, an Alatom, a Fe atom, a Cu atom, a Pt atom, a Pb atom, an Au atom or an Agatom, more preferably an Sn atom, an Si atom, a Zr atom, a Ti atom, a Geatom, an Al atom, a Pb atom or a Zn atom, and further preferably an Snatom, an Si atom, a Zr atom, a Ti atom or a Ge atom. In the generalformula (3), X₁ and X₂ each independently represent a sulfur atom or anoxygen atom. In consideration of the desired effect of the presentinvention, i.e., a high refractive index, as X₁ and X₂, preferably usedis a sulfur atom.

In the general formula (3), R₁ represents a divalent organic group.

Examples of the divalent organic group include a chained or cyclicaliphatic group, an aromatic group or an aromatic-aliphatic group,preferably a chained aliphatic group having 1 to 20 carbon atoms, acyclic aliphatic group having 3 to 20 carbon atoms, an aromatic grouphaving 5 to 20 carbon atoms and an aromatic-aliphatic group having 6 to20 carbon atoms.

More specifically, this divalent organic group is a chained or cyclicaliphatic group, an aromatic group or an aromatic-aliphatic group,preferably a substituted or unsubstituted chained or cyclic aliphaticgroup having 1 to 20 carbon atoms such as a methylene group, an ethylenegroup, a 1,2-dichloroethylene group, a trimethylene group, atetramethylene group, a pentamethylene group, a cyclopentylene group, ahexamethylene group, a cyclohexylene group, a heptamethylene group, anoctamethylene group, a nonamethylene group, a decamethylene group, anundecamethylene group, a dodecamethylene group, a tridecamethylenegroup, a tetradecamethylene group, a pentadecamethylene group and thelike;

a substituted or unsubstituted aromatic group having 5 to 20 carbonatoms such as a phenylene group, a chlorophenylene group, a naphthylenegroup, an indenylene group, an anthracenylene group, a fluorenylenegroup and the like; anda substituted or unsubstituted aromatic-aliphatic group having 6 to 20carbon atoms such as a —C₆H₄—CH₂— group, a —CH₂—C₆H₄—CH₂— group, a—CH₂—C₆H₃ (Cl)—CH₂— group, a —C₁₀H₆—CH₂— group, a —CH₂—C₁₀H₆—CH₂— group,a —CH₂CH₂—C₆H₄—CH₂CH₂— group and the like,and more preferably a substituted or unsubstituted chained or cyclicaliphatic group having 1 to 6 carbon atoms such as a methylene group, anethylene group, a 1,2-dichloroethylene group, a trimethylene group, acyclopentylene group, a cyclohexylene group and the like;a substituted or unsubstituted aromatic group having 5 to 15 carbonatoms such as a phenylene group, a chlorophenylene group, a naphthylenegroup, an indenylene group, an anthracenylene group, a fluorenylenegroup and the like; anda substituted or unsubstituted aromatic-aliphatic group having 6 to 15carbon atoms such as a —C₆H₄—CH₂— group, a —CH₂—C₆H₄—CH₂— group, a—CH₂—C₆H₃ (Cl)—CH₂— group, a —C₁₀H₆—CH₂— group, a —CH₂—C₁₀H₆—CH₂— group,a —CH₂CH₂—C₆H₄—CH₂CH₂— group and the like.

This divalent organic group may contain a heteroatom except for a carbonatom or a hydrogen group in the group. Examples of the heteroatominclude an oxygen atom or a sulfur atom. Considering the desired effectof the present invention, a sulfur atom is preferable.

In the general formula (3), m represents an integer of 0 or 1 or more.

Examples of m are preferably an integer of 0 to 4, more preferably aninteger of 0 to 2, and further preferably an integer of 0 or 1.

In the general formula (3), n represents a valence of a metal atom M.

In the general formula (3), p represents an integer of 1 to n.

Examples of p preferably include n, n−1 or n−2 and more preferably n orn−1.

In the general formula (3), q represents an integer of 1 to (n−p).

In the general formula (3), Y's each independently represents aninorganic or organic residue.

Examples of the residue include a halogen atom, a hydroxyl group, analkoxy group, an alkylthio group, an aryloxy group and an arylthiogroup. Of these, a halogen atom, an alkoxy group, an alkylthio group, anaryloxy group and an arylthio group are specifically the same as ahalogen atom, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group in A₁ to A₁₀ of the general formulae (1) and (2).Furthermore, when q is an integer of 2 or more, Y's may, of course, bebonded to one another for forming a ring structure through theintermediary of the metal atom M.

The compound represented by the general formula (3) is specificallyexemplified in the following Table 3. However, the compound is notrestricted to the following.

TABLE 3-1 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-1 Sn 4 4 0 0 S— — — 3-2 Sn 4 4 0 0 O — — — — — 3-3 Sn 4 4 0 1 S S CH₂ — — — 3-4 Sn 4 40 1 O S CH₂ — — — 3-5 Sn 4 4 0 1 S O CH₂ — — — 3-6 Sn 4 4 0 1 O O CH₂ —— — 3-7 Sn 4 4 0 1 S S C₂H₄ — — — 3-8 Sn 4 4 0 1 O S C₂H₄ — — — 3-9 Sn 44 0 1 S O C₂H₄ — — — 3-10 Sn 4 4 0 1 O O C₂H₄ — — — 3-11 Sn 4 4 0 1 S S

— — — 3-12 Sn 4 4 0 1 O S

— — — 3-13 Sn 4 4 0 1 S O

— — — 3-14 Sn 4 4 0 1 O O

— — — 3-15 Sn 4 4 0 1 S S

— — — 3-16 Sn 4 4 0 1 O S

— — — 3-17 Sn 4 4 0 1 S O

— — — 3-18 Sn 4 4 0 1 O O

— — — 3-19 Sn 4 4 0 1 S S

— — — 3-20 Sn 4 4 0 1 O S

— — — 3-21 Sn 4 4 0 1 S O

— — — 3-22 Sn 4 4 0 1 O O

— — — 3-23 Sn 4 4 0 1 S S

— — — 3-24 Sn 4 4 0 1 O S

— — — 3-25 Sn 4 4 0 1 S O

— — — 3-26 Sn 4 4 0 1 O O

— — — 3-27 Sn 4 4 0 1 S S

— — — 3-28 Sn 4 4 0 1 O S

— — — 3-29 Sn 4 4 0 1 S O

— — — 3-30 Sn 4 4 0 1 O O

— — — 3-31 Sn 4 4 0 1 S S

— — — 3-32 Sn 4 4 0 1 O S

— — — 3-33 Sn 4 4 0 1 S O

— — — 3-34 Sn 4 4 0 1 O O

— — — 3-35 Sn 4 3 1 0 S — — CH₃ — — 3-36 Sn 4 3 1 0 O — — CH₃ — — 3-37Sn 4 3 1 0 S — — C₂H₅ — — 3-38 Sn 4 3 1 0 O — — C₂H₅ — — 3-39 Sn 4 3 1 0S — — C₃H₇ — — 3-40 Sn 4 3 1 0 O — — C₃H₇ — — 3-41 Sn 4 3 1 0 S — — C₄H₉— — 3-42 Sn 4 3 1 0 O — — C₄H₉ — — 3-43 Sn 4 3 1 0 S — — C₆H₅ — — 3-44Sn 4 3 1 0 O — — C₆H₅ — — 3-45 Sn 4 2 2 0 S — — CH₃ CH₃ — 3-46 Sn 4 2 20 O — — CH₃ CH₃ — 3-47 Sn 4 2 2 0 S — — C₂H₅ C₂H₅ — 3-48 Sn 4 2 2 0 O —— C₂H₅ C₂H₅ — 3-49 Sn 4 2 2 0 S — — C₃H₇ C₃H₇ — 3-50 Sn 4 2 2 0 O — —C₃H₇ C₃H₇ —

TABLE 3-2 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-51 Sn 4 2 2 0 S— — C₄H₉ C₄H₉ — 3-52 Sn 4 2 2 0 O — — C₄H₉ C₄H₉ — 3-53 Sn 4 2 2 0 S — —C₆H₅ C₆H₅ — 3-54 Sn 4 2 2 0 O — — C₆H₅ C₆H₅ — 3-55 Sn 4 1 3 0 S — — CH₃CH₃ CH₃ 3-56 Sn 4 1 3 0 O — — CH₃ CH₃ CH₃ 3-57 Sn 4 1 3 0 S — — C₂H₅C₂H₅ C₂H₅ 3-58 Sn 4 1 3 0 O — — C₂H₅ C₂H₅ C₂H₅ 3-59 Sn 4 1 3 0 S — —C₃H₇ C₃H₇ C₃H₇ 3-60 Sn 4 1 3 0 O — — C₃H₇ C₃H₇ C₃H₇ 3-61 Sn 4 1 3 0 S —— C₄H₉ C₄H₉ C₄H₉ 3-62 Sn 4 1 3 0 O — — C₄H₉ C₄H₉ C₄H₉ 3-63 Sn 4 1 3 0 S— — C₆H₅ C₆H₅ C₆H₅ 3-64 Sn 4 1 3 0 O — — C₆H₅ C₆H₅ C₆H₅ 3-65 Sn 4 3 1 0S — — SCH₃ — — 3-66 Sn 4 3 1 0 O — — SCH₃ — — 3-67 Sn 4 3 1 0 S — —SC₂H₅ — — 3-68 Sn 4 3 1 0 O — — SC₂H₅ — — 3-69 Sn 4 3 1 0 S — — SC₆H₅ —— 3-70 Sn 4 3 1 0 O — — SC₆H₅ — — 3-71 Sn 4 2 2 0 S — — SC₂H₄S — 3-72 Sn4 2 2 0 O — — SC₂H₄S — 3-73 Sn 4 2 2 0 S — — SC₃H₆S — 3-74 Sn 4 2 2 0 O— — SC₃H₆S — 3-75 Sn 4 2 2 0 S — — SC₂H₄SC₂H₄S — 3-76 Sn 4 2 2 0 O — —SC₂H₄SC₂H₄S — 3-77 Sn 4 3 1 1 S S CH₂ CH₃ — — 3-78 Sn 4 3 1 1 O S CH₂CH₃ — — 3-79 Sn 4 3 1 1 S O CH₂ CH₃ — — 3-80 Sn 4 3 1 1 O O CH₂ CH₃ — —3-81 Sn 4 3 1 1 S S C₂H₄ CH₃ — — 3-82 Sn 4 3 1 1 O S C₂H₄ CH₃ — — 3-83Sn 4 3 1 1 S O C₂H₄ CH₃ — — 3-84 Sn 4 3 1 1 O O C₂H₄ CH₃ — — 3-85 Sn 4 31 1 S S

CH₃ — — 3-86 Sn 4 3 1 1 O S

CH₃ — — 3-87 Sn 4 3 1 1 S O

CH₃ — — 3-88 Sn 4 3 1 1 O O

CH₃ — — 3-89 Sn 4 3 1 1 S S

CH₃ — — 3-90 Sn 4 3 1 1 O S

CH₃ — — 3-91 Sn 4 3 1 1 S O

CH₃ — — 3-92 Sn 4 3 1 1 O O

CH₃ — — 3-93 Sn 4 3 1 1 S S

CH₃ — — 3-94 Sn 4 3 1 1 O S

CH₃ — — 3-95 Sn 4 3 1 1 S O

CH₃ — — 3-96 Sn 4 3 1 1 O O

CH₃ — — 3-97 Sn 4 3 1 1 S S

CH₃ — — 3-98 Sn 4 3 1 1 O S

CH₃ — — 3-99 Sn 4 3 1 1 S O

CH₃ — — 3-100 Sn 4 3 1 1 O O

CH₃ — —

TABLE 3-3 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-101 Sn 4 3 1 1S S

CH₃ — — 3-102 Sn 4 3 1 1 O S

CH₃ — — 3-103 Sn 4 3 1 1 S O

CH₃ — — 3-104 Sn 4 3 1 1 O O

CH₃ — — 3-105 Sn 4 3 1 1 S S

CH₃ — — 3-106 Sn 4 3 1 1 O S

CH₃ — — 3-107 Sn 4 3 1 1 S O

CH₃ — — 3-108 Sn 4 3 1 1 O O

CH₃ — — 3-109 Sn 4 3 1 1 S S CH₂ C₆H₅ — — 3-110 Sn 4 3 1 1 O S CH₂ C₆H₅— — 3-111 Sn 4 3 1 1 S O CH₂ C₆H₅ — — 3-112 Sn 4 3 1 1 O O CH₂ C₆H₅ — —3-113 Sn 4 3 1 1 S S C₂H₄ C₆H₅ — — 3-114 Sn 4 3 1 1 O S C₂H₄ C₆H₅ — —3-115 Sn 4 3 1 1 S O C₂H₄ C₆H₅ — — 3-116 Sn 4 3 1 1 O O C₂H₄ C₆H₅ — —3-117 Sn 4 3 1 1 S S

C₆H₅ — — 3-118 Sn 4 3 1 1 O S

C₆H₅ — — 3-119 Sn 4 3 1 1 S O

C₆H₅ — — 3-120 Sn 4 3 1 1 O O

C₆H₅ — — 3-121 Sn 4 3 1 1 S S

C₆H₅ — — 3-122 Sn 4 3 1 1 O S

C₆H₅ — — 3-123 Sn 4 3 1 1 S O

C₆H₅ — — 3-124 Sn 4 3 1 1 O O

C₆H₅ — — 3-125 Sn 4 3 1 1 S S

C₆H₅ — — 3-126 Sn 4 3 1 1 O S

C₆H₅ — — 3-127 Sn 4 3 1 1 S O

C₆H₅ — — 3-128 Sn 4 3 1 1 O O

C₆H₅ — — 3-129 Sn 4 3 1 1 S S

C₆H₅ — — 3-130 Sn 4 3 1 1 O S

C₆H₅ — — 3-131 Sn 4 3 1 1 S O

C₆H₅ — — 3-132 Sn 4 3 1 1 O O

C₆H₅ — — 3-133 Sn 4 3 1 1 S S

C₆H₅ — — 3-134 Sn 4 3 1 1 O S

C₆H₅ — — 3-135 Sn 4 3 1 1 S O

C₆H₅ — — 3-136 Sn 4 3 1 1 O O

C₆H₅ — — 3-137 Sn 4 3 1 1 S S

C₆H₅ — — 3-138 Sn 4 3 1 1 O S

C₆H₅ — — 3-139 Sn 4 3 1 1 S O

C₆H₅ — — 3-140 Sn 4 3 1 1 O O

C₆H₅ — — 3-141 Si 4 4 0 0 S — — — — — 3-142 Si 4 4 0 0 O — — — — — 3-143Si 4 4 0 1 S S CH₂ — — — 3-144 Si 4 4 0 1 O S CH₂ — — — 3-145 Si 4 4 0 1S O CH₂ — — — 3-146 Si 4 4 0 1 O O CH₂ — — —

TABLE 3-4 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-147 Si 4 4 0 1S S C₂H₄ — — — 3-148 Si 4 4 0 1 O S C₂H₄ — — — 3-149 Si 4 4 0 1 S O C₂H₄— — — 3-150 Si 4 4 0 1 O O C₂H₄ — — — 3-151 Si 4 4 0 1 S S

— — — 3-152 Si 4 4 0 1 O S

— — — 3-153 Si 4 4 0 1 S O

— — — 3-154 Si 4 4 0 1 O O

— — — 3-155 Si 4 4 0 1 S S

— — — 3-156 Si 4 4 0 1 O S

— — — 3-157 Si 4 4 0 1 S O

— — — 3-158 Si 4 4 0 1 O O

— — — 3-159 Si 4 4 0 1 S S

— — — 3-160 Si 4 4 0 1 O S

— — — 3-161 Si 4 4 0 1 S O

— — — 3-162 Si 4 4 0 1 O O

— — — 3-163 Si 4 4 0 1 S S

— — — 3-164 Si 4 4 0 1 O S

— — — 3-165 Si 4 4 0 1 S O

— — — 3-166 Si 4 4 0 1 O O

— — — 3-167 Si 4 4 0 1 S S

— — — 3-168 Si 4 4 0 1 O S

— — — 3-169 Si 4 4 0 1 S O

— — — 3-170 Si 4 4 0 1 O O

— — — 3-171 Si 4 4 0 1 S S

— — — 3-172 Si 4 4 0 1 O S

— — — 3-173 Si 4 4 0 1 S O

— — — 3-174 Si 4 4 0 1 O O

— — — 3-175 Si 4 3 1 0 S — — CH₃ — — 3-176 Si 4 3 1 0 O — — CH₃ — —3-177 Si 4 3 1 0 S — — C₂H₅ — — 3-178 Si 4 3 1 0 O — — C₂H₅ — — 3-179 Si4 3 1 0 S — — C₆H₅ — — 3-180 Si 4 3 1 0 O — — C₆H₅ — — 3-181 Si 4 2 2 0S — — CH₃ CH₃ — 3-182 Si 4 2 2 0 O — — CH₃ CH₃ — 3-183 Si 4 2 2 0 S — —C₆H₅ C₆H₅ — 3-184 Si 4 2 2 0 O — — C₆H₅ C₆H₅ — 3-185 Si 4 1 3 0 S — —C₆H₅ C₆H₅ C₆H₅ 3-186 Si 4 1 3 0 O — — C₆H₅ C₆H₅ C₆H₅ 3-187 Si 4 2 2 0 S— — SC₂H₄S — 3-188 Si 4 2 2 0 O — — SC₂H₄S — 3-189 Si 4 2 2 0 S — —SC₃H₆S — 3-190 Si 4 2 2 0 O — — SC₃H₆S — 3-191 Si 4 2 2 0 S — —SC₂H₄SC₂H₄S — 3-192 Si 4 2 2 0 O — — SC₂H₄SC₂H₄S — 3-193 Ge 4 4 0 0 S —— — — — 3-194 Ge 4 4 0 0 O — — — — — 3-195 Ge 4 4 0 1 S S CH₂ — — —3-196 Ge 4 4 0 1 O S CH₂ — — — 3-197 Ge 4 4 0 1 S O CH₂ — — — 3-198 Ge 44 0 1 O O CH₂ — — — 3-199 Ge 4 4 0 1 S S C₂H₄ — — — 3-200 Ge 4 4 0 1 O SC₂H₄ — — —

TABLE 3-5 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-201 Ge 4 4 0 1S O C₂H₄ — — — 3-202 Ge 4 4 0 1 O O C₂H₄ — — — 3-203 Ge 4 4 0 1 S S

— — — 3-204 Ge 4 4 0 1 O S

— — — 3-205 Ge 4 4 0 1 S O

— — — 3-206 Ge 4 4 0 1 O O

— — — 3-207 Ge 4 4 0 1 S S

— — — 3-208 Ge 4 4 0 1 O S

— — — 3-209 Ge 4 4 0 1 S O

— — — 3-210 Ge 4 4 0 1 O O

— — — 3-211 Ge 4 4 0 1 S S

— — — 3-212 Ge 4 4 0 1 O S

— — — 3-213 Ge 4 4 0 1 S O

— — — 3-214 Ge 4 4 0 1 O O

— — — 3-215 Ge 4 4 0 1 S S

— — — 3-216 Ge 4 4 0 1 O S

— — — 3-217 Ge 4 4 0 1 S O

— — — 3-218 Ge 4 4 0 1 O O

— — — 3-219 Ge 4 4 0 1 S S

— — — 3-220 Ge 4 4 0 1 O S

— — — 3-221 Ge 4 4 0 1 S O

— — — 3-222 Ge 4 4 0 1 O O

— — — 3-223 Ge 4 4 0 1 S S

— — — 3-224 Ge 4 4 0 1 O S

— — — 3-225 Ge 4 4 0 1 S O

— — — 3-226 Ge 4 4 0 1 O O

— — — 3-227 Ge 4 3 1 0 S — CH₃ — — — 3-228 Ge 4 3 1 0 O — CH₃ — — —3-229 Ge 4 3 1 0 S — C₂H₅ — — — 3-230 Ge 4 3 1 0 O — C₂H₅ — — — 3-231 Ge4 3 1 0 S — C₆H₅ — — — 3-232 Ge 4 3 1 0 O — C₆H₅ — — — 3-233 Ge 4 2 2 0S — CH₃ CH₃ — — 3-234 Ge 4 2 2 0 O — CH₃ CH₃ — — 3-235 Ge 4 2 2 0 S —C₆H₅ C₆H₅ — — 3-236 Ge 4 2 2 0 O — C₆H₅ C₆H₅ — — 3-237 Ge 4 1 3 0 S —C₆H₅ C₆H₅ C₆H₅ — 3-238 Ge 4 1 3 0 O — C₆H₅ C₆H₅ C₆H₅ — 3-239 Ge 4 2 2 0S — SC₂H₄S — — 3-240 Ge 4 2 2 0 O — SC₂H₄S — — 3-241 Ge 4 2 2 0 S —SC₃H₆S — — 3-242 Ge 4 2 2 0 O — SC₃H₆S — — 3-243 Ge 4 2 2 0 S —SC₂H₄SO₂H₄S — — 3-244 Ge 4 2 2 0 O — SC₂H₄SO₂H₄S — — 3-245 Zn 2 2 0 0 S— — — — — 3-246 Zn 2 2 0 0 O — — — — — 3-247 Zr 4 4 0 0 S — — — — —3-248 Zr 4 4 0 0 O — — — — — 3-249 Zr 4 2 2 0 S — — cyclopentadienylcyclopentadienyl — 3-250 Zr 4 2 2 0 O — — cyclopentadienylcyclopentadienyl —

TABLE 3-6 [Concrete examples of the compound represented by the generalformula (3)] Compound Nos. M n p q m X1 X2 R1 Y1 Y2 Y3 3-251 Zr 4 4 0 1S S CH₂ — — — 3-252 Zr 4 4 0 1 O S CH₂ — — — 3-253 Zr 4 4 0 1 S O CH₂ —— — 3-254 Zr 4 4 0 1 O O CH₂ — — — 3-255 Zr 4 4 0 1 S S C₂H₄ — — — 3-256Zr 4 4 0 1 O S C₂H₄ — — — 3-257 Zr 4 4 0 1 S O C₂H₄ — — — 3-258 Zr 4 4 01 O O C₂H₄ — — — 3-259 Zr 4 2 2 1 S S CH₂ cyclopentadienylcyclopentadienyl — 3-260 Zr 4 2 2 1 O S CH₂ cyclopentadienylcyclopentadienyl — 3-261 Zr 4 2 2 1 S O CH₂ cyclopentadienylcyclopentadienyl — 3-262 Zr 4 2 2 1 O O CH₂ cyclopentadienylcyclopentadienyl — 3-263 Zr 4 2 2 1 S S C₂H₄ cyclopentadienylcyclopentadienyl — 3-264 Zr 4 2 2 1 O S C₂H₄ cyclopentadienylcyclopentadienyl — 3-265 Zr 4 2 2 1 S O C₂H₄ cyclopentadienylcyclopentadienyl — 3-266 Zr 4 2 2 1 O O C₂H₄ cyclopentadienylcyclopentadienyl — 3-267 Ti 4 4 0 0 S — — — — — 3-268 Ti 4 4 0 0 O — — —— — 3-269 Ti 4 2 2 0 S — — cyclopentadienyl cyclopentadienyl — 3-270 Ti4 2 2 0 O — — cyclopentadienyl cyclopentadienyl — 3-271 Ti 4 4 0 1 S SCH₂ — — — 3-272 Ti 4 4 0 1 O S CH₂ — — — 3-273 Ti 4 4 0 1 S O CH₂ — — —3-274 Ti 4 4 0 1 O O CH₂ — — — 3-275 Ti 4 4 0 1 S S C₂H₄ — — — 3-276 Ti4 4 0 1 O S C₂H₄ — — — 3-277 Ti 4 4 0 1 S O C₂H₄ — — — 3-278 Ti 4 4 0 1O O C₂H₄ — — — 3-279 Ti 4 2 2 1 S S CH₂ cyclopentadienylcyclopentadienyl — 3-280 Ti 4 2 2 1 O S CH₂ cyclopentadienylcyclopentadienyl — 3-281 Ti 4 2 2 1 S O CH₂ cyclopentadienylcyclopentadienyl — 3-282 Ti 4 2 2 1 O O CH₂ cyclopentadienylcyclopentadienyl — 3-283 Ti 4 2 2 1 S S C₂H₄ cyclopentadienylcyclopentadienyl — 3-284 Ti 4 2 2 1 O S C₂H₄ cyclopentadienylcyclopentadienyl — 3-285 Ti 4 2 2 1 S O C₂H₄ cyclopentadienylcyclopentadienyl — 3-286 Ti 4 2 2 1 O O C₂H₄ cyclopentadienylcyclopentadienyl — 3-287 Pb 4 4 0 0 S — — — — — 3-288 Pb 4 4 0 0 O — — —— — 3-289 Al 3 3 0 0 S — — — — — 3-290 Al 3 3 0 0 O — — — — — 3-291 Al 32 1 0 S — — SCH₃ — — 3-292 Al 3 2 1 0 O — — SCH₃ — — 3-293 Al 3 2 1 0 S— — SC₂H₅ — — 3-294 Al 3 2 1 0 O — — SC₂H₅ — — 3-295 Al 3 2 1 0 S — —SC₆H₅ — — 3-296 Al 3 2 1 0 O — — SC₆H₅ — — 3-297 Al 3 1 2 0 S — — SC₂H₄S— 3-298 Al 3 1 2 0 O — — SC₂H₄S — 3-299 Al 3 1 2 0 S — — SC₂H₄SC₂H₄S —3-300 Al 3 1 2 0 O — — SC₂H₄SC₂H₄S —

The compound represented by the general formula (3) of the presentinvention is typically prepared by the reaction of a halide of the metalatom M represented by the general formula (5) with a hydroxy compound ora thiol compound having the thietane group represented by the generalformula (6),

wherein, in the formula, M, n, p and Yq are the same as M, n, p and Yqin the general formula (3); and Z represents a halogen atom,

wherein, in the formula, X₁, X₂, R₁ and m are the same as X₁, X₂, R₁ andm in the general formula (3).

The compound represented by the general formula (5) is available as anindustrial raw material or a research reagent. The compound representedby the general formula (6) is known in the art, and is prepared by amethod as described, for example, in Japanese Patent Laid-Open No.2003-327583.

The reaction can be carried out without a solvent or in the presence ofa solvent, which is inactive to the reaction.

The solvents are not particularly limited as long as they are inactiveto the reaction. Examples thereof include hydrocarbon solvents such aspetroleum ether, hexane, benzene, toluene, xylene, mesitylene and thelike; ether solvents such as diethyl ether, tetrahydrofuran, diethyleneglycol dimethyl ether and the like; ketone solvents such as acetone,methyl ethyl ketone, methyl isobutyl ketone and the like; ester solventssuch as ethyl acetate, butyl acetate, amyl acetate and the like;chlorine-containing solvents such as methylene chloride, chloroform,chlorobenzene, dichlorobenzene and the like; polar aprotic solvents suchas N,N-dimethylformamide, N,N-dimethylacetamide,N,N-dimethylimidazolidinone, dimethyl sulfoxide and the like; water andthe like.

The reaction temperature is not particularly limited, but it is usuallyin the range of from −78° C. to 200° C. and preferably from −78° C. to100° C.

The reaction temperature affects the reaction time, but it is usuallyfrom several minutes to 100 hours.

The amount of the compound represented by the general formula (5) andthe compound represented by the general formula (6) used in the reactionis not particularly limited, but the amount of the compound representedby the general formula (6) is usually from 0.01 to 100 mole, preferablyfrom 0.1 to 50 mole and more preferably from 0.5 to 20 mole, based on 1mole of the halogen atom contained in the compound represented by thegeneral formula (5).

When carrying out the reaction, it is preferable to use a basic compoundas a capturing agent of the generated halogenated hydrogen foreffectively carrying out the reaction. Examples of the basic compoundinclude inorganic bases such as sodium hydroxide, potassium hydroxide,lithium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, sodium bicarbonate, potassium bicarbonate, lithiumbicarbonate, magnesium hydroxide, calcium hydroxide and the like; andorganic bases such as pyridine, triethylamine, dimethylaniline,diethylaniline, 1,8-diazabicyclo[5,4,0]-7-undecene and the like.

The polymerizable composition of the present invention comprises thecompound containing one or two or more thietane groups and a metal atomin a molecule such as the compound typically represented by the generalformula (3) (hereinafter referred to as a metal-containing thietanecompound) as a polymerizable compound, and comprises a polymerizationcatalyst as needed.

In this case, as the metal-containing thietane compound, the compoundsas described above may be used singly or as the metal-containingthietane compound, a plurality of other compounds may, of course, beused together.

The content of the metal-containing thietane compound occupied in thetotal weight of the polymerizable compound contained in thepolymerizable composition of the present invention is not particularlylimited, but it is usually not less than 10 weight %, preferably notless than 30 weight %, more preferably not less than 50 weight % andfurther preferably not less than 70 weight %.

The polymerization catalyst to be used in the polymerizable compositionof the present invention as needed is not particularly limited, andpolymerization catalysts, known in the art as described, for example, inJapanese Patent Laid-Open No. 2003-327583 can be used. Examples of thepolymerization catalyst include an amine compound, a phosphine compound,an organic acid and its derivatives (salt, ester or acid anhydride andthe like), an inorganic acid, onium salt compounds such as a quaternaryammonium salt compound, a quaternary phosphonium salt compound, atertiary sulfonium salt compound, a secondary iodonium salt compound andthe like, a Lewis acid compound, a radical polymerization catalyst, acationic polymerization catalyst and the like.

The amount of the polymerization catalyst used is affected by thecomposition of the polymerizable composition, polymerization conditionsand the like, so it is not particularly limited. It is from 0.0001 to 10weight parts, preferably from 0.001 to 5 weight parts, and morepreferably from 0.005 to 3 weight parts, based on 100 weight of thetotal polymerizable compound contained in the polymerizable composition.

The polymerizable composition of the present invention may contain otherpolymerizable compounds in addition to the metal-containing thietanecompound in the ranges in which the desired effect of the presentinvention is not damaged.

Examples of the polymerizable compound include various polymerizablemonomers or polymerizable oligomers, known in the art. Examples thereofinclude a (meth)acrylic acid ester compound, a vinyl compound, an epoxycompound, an episulfide compounds, an oxetane compound, a thietanecompound and the like.

The amount of the other polymerizable compounds occupied in the totalweight of the polymerizable compounds contained in the polymerizablecomposition of the present invention is not particularly limited, but itis usually not more than 90 weight %, preferably not more than 70 weight%, more preferably not more than 50 weight %, and further preferably notmore than 30 weight %

A typical process for producing the polymerizable composition of thepresent invention comprises using the metal-containing thietane compoundand various known polymerizable compounds as described above dependingon the intended use together, adding the aforementioned polymerizationcatalyst as further needed, and then mixing and dissolving the resultingmixture. The polymerizable composition is preferably polymerized afterthoroughly degassing under a reduced pressure as required, and filteringoff impurities, foreign substances or the like before polymerization.

When producing the polymerizable composition, various known additivescan also be added in the ranges in which the effect of the presentinvention is not damaged. Examples of the additive include an internalrelease agent, a photostabilizer, an ultraviolet absorbent, ananti-oxidant, coloring pigments (for example, cyanine green, cyanineblue and the like), dyes, a flowability regulator, filler and the like.

The resin and the optical component comprising such a resin of thepresent invention are obtained by polymerization of the aforementionedpolymerizable composition. Such polymerization is suitably carried outaccording to various methods, known in the art, used when producingplastic lenses. A typical method includes a casting polymerization.

Namely, the polymerizable composition of the present invention producedby the above method is degassed under a reduced pressure or filtered offas required, and then the polymerizable composition is poured into amold, and heated as required for carrying out polymerization. In thiscase, it is preferable to carry out polymerization by slowly heatingfrom a low temperature to a high temperature.

The mold is composed of, for example, two pieces of mirrorsurface-ground molds via a gasket made of polyethylene, an ethylenevinyl acetate copolymer, polyvinyl chloride and the like. Typicalexamples of the mold include, though not restricted to, combined moldssuch as glass and glass, glass and plastic plate, glass and metal plate,and the like. The mold may comprise two pieces of molds fixed by a tapesuch as a polyester adhesive tape or the like. In addition, a knownmethod such as the mold release process may be performed for the mold,as needed.

When carrying out casting polymerization, the polymerization temperatureis affected by the polymerization conditions such as the kind ofpolymerization initiator and the like, and is not particularly limited.But, it is usually from −50° C. to 200° C., preferably from −20° C. to170° C., and more preferably from 0 to 150° C.

The polymerization temperature affects the polymerization time, but itis usually from 0.01 to 200 hours and preferably from 0.05 to 100 hours.Polymerization can also be carried out in combination of severaltemperatures by conducting low temperature, temperature elevation,temperature dropping and the like as required.

Furthermore, the polymerizable composition of the present invention canbe polymerized by applying the active energy line such as an electronbeam, ultraviolet light, visible light or the like. At this time, aradical polymerization catalyst or a cationic polymerization catalystfor initiating polymerization by the active energy line is used asrequired.

After the thus-obtained optical lens is cured, it may be subjected to anannealing process as required. Furthermore, for purposes ofanti-reflection, high hardness grant, wear resistance improvement,anti-fogging property grant or fashionability grant, various knownphysical or chemical processes such as surface polishing, antistaticprocess, hard coat process, non-reflective coat process, anti-reflectiveprocess, tinting process, photochromic process (for example,photochromic lens process and the like) and the like may be performed asneeded.

Meanwhile, the resin cured product and optical component obtained bypolymerization of the polymerizable composition of the present inventionhave high transparency, good heat resistance and mechanical strength,while attaining a high refractive index (nd) exceeding 1.7.

Examples of the optical component of the present invention includevarious plastic lenses such as a spectacle lens for vision correction, alens for cameras, a fresnel lens for liquid crystal projectors, alenticular lens, a contact lens and the like, a sealing material forlight emitting diodes, an optical waveguide, an optical adhesive usedfor the junction of an optical lens or an optical waveguide, ananti-reflection film to be used for optical lenses, transparent coatingor transparent substrate used for liquid crystal display members(substrate, light guiding plate, film, sheet and the like) and the like.

EXAMPLES

The present invention is now more specifically illustrated below withreference to Preparation Examples and Examples. However, the presentinvention is not limited to these Examples.

Reference Preparation Example 1

According to the method as described in Japanese Patent Laid-Open No.2003-327583, 3-thiethanol was synthesized. The resulting 3-thiethanolwas used to synthesize 3-mercaptothietane. Namely, 190 g of thiourea,253 g of a 35% hydrochloric acid solution and 250 g of water wereintroduced into a reactor equipped with a stirrer and a thermometer, andstirred. While stirring, 156 g of 3-thiethanol was added dropwise to thereaction solution over 1 hour. The resulting solution was stirred andreacted at 30° C. for 24 hours, and then 177 g of 24% ammonia water wasadded dropwise thereto over 1 hour. The solution was further reacted at30° C. for 15 hours, and then allowed to stand for taking out an organiclayer (lower layer) to obtain 134 g of a coarse composition. Theresulting coarse composition was distilled off under a reduced pressureto collect a fraction with a boiling point of 40° C./106 Pa to obtainthe desired product of a colorless transparent liquid, i.e.,3-mercaptothietane.

Example 1 Preparation of a Compound Represented by the Compound No. 3-1in Table 3-1

11.04 g (0.104 mole) of 3-mercaptothietane was introduced to 150 g ofdried methylene chloride and cooled down to −30° C. 11.87 g (0.15 mole)of dried pyridine was added thereto at the same temperature and stirredfor 5 minutes. Subsequently, 25 ml (corresponding to 0.025 mole of tintetrachloride) of a 1N methylene chloride solution of tin tetrachloridewas inserted dropwise thereto at −30° C. over 2 hours. After thedropwise addition was completed, the reaction solution was subjected toa temperature elevation to −20° C. and further stirred at thetemperature for 4 hours. 50 ml of 2N HCl was added to the reactionmixture, and the organic layer and the water layer were separated. Thewater layer was extracted twice using 30 ml of toluene and toluene wasadded to the organic layer. The organic layer with toluene added theretowas washed with 50 ml of 2N HCl and 50 ml of pure water twicerespectively, and then dried over anhydrous magnesium sulfate. Methylenechloride and toluene were distilled off from the extract to obtain acoarse composition. The resulting coarse composition was purified bysilica gel column chromatography with a development solvent of hexane toobtain 10.10 g (Yield: 75%) of a compound represented by the CompoundNo. 3-1 in Table 3-1. ¹H-NMR data are shown in the following (solvent:CDCl₃, internal standard substance: TMS): δ 3.43 (16H), δ 4.70 (4H).

Example 2 Preparation of a Compound Represented by the Compound No. 3-1in Table 3-1 (Another Method)

11.15 g (0.105 mole) of 3-mercaptothietane was introduced to 50 g ofpure water. Subsequently, 41.2 g (0.103 mole) of a 10% NaOH aqueoussolution was introduced dropwise at room temperature over 40 minutes.Then, the reaction solution was subjected to a temperature elevation to30° C. and 65.2 g (corresponding to 0.025 mole of tin tetrachloride) ofan aqueous solution of 10% tin tetrachloride was inserted dropwise atthe same temperature over 4 hours. After the dropwise addition wascompleted, the solution was further stirred at the same temperature for2 hours. 100 ml of chloroform was added to the reaction mixture, and theorganic layer and the water layer were separated. The organic layer waswashed with 100 ml of pure water twice, and then dried over anhydroussodium sulfate. The solvent was distilled off from the extract to obtain13.40 g (Yield: 99%) of a compound represented by the Compound No. 3-1in Table 3-1.

Example 3 Preparation of a Compound Represented by the Compound No. 3-35in Table 3-1

6.69 g (0.063 mole) of 3-mercaptothietane was introduced to 30 g of purewater. Subsequently, 24.8 g (0.062 mole) of a 10% NaOH aqueous solutionwas introduced dropwise at room temperature over 40 minutes. Then, thereaction solution was subjected to a temperature elevation to 30° C. and48.0 g (corresponding to 0.020 mole of methyl tin trichloride) of anaqueous solution of 10% methyl tin trichloride was inserted dropwise atthe same temperature over 4 hours. After the dropwise addition wascompleted, the solution was further stirred at the same temperature for2 hours. 100 ml of chloroform was added to the reaction mixture, and theorganic layer and the water layer were separated. The organic layer waswashed with 100 ml of pure water twice, and then dried over anhydroussodium sulfate. The solvent was distilled off from the extract to obtain8.90 g (Yield: 99%) of a compound represented by the Compound No. 3-35in Table 3-1. ¹H-NMR data are shown in the following (solvent: CDCl₃,internal standard substance: TMS): δ 1.12 (3H), δ 3.38 (6H), δ 3.46(6H), δ 4.62 (3H).

Example 4 Preparation of a Compound Represented by the Compound No. 3-41in Table 3-1

9.80 g (Yield: 100%) of a compound represented by the Compound No. 3-41in Table 3-1 was obtained by carrying out the same operation as inExample 3, except that butyl tin trichloride was used instead of methyltin trichloride. ¹H-NMR data are shown in the following (solvent: CDCl₃,internal standard substance: TMS): δ 0.93 (3H), δ 1.39 (2H), δ 1.75(4H), δ 3.39 (12H), δ 4.64 (3H).

Example 5 Preparation of a Compound Represented by the Compound No. 3-43in Table 3-1

8.28 g (Yield: 81%) of a compound represented by the Compound No. 3-43in Table 3-1 was obtained by carrying out the same operation as inExample 3, except that phenyl tin trichloride was used instead of methyltin trichloride. ¹H-NMR data are shown in the following (solvent:DMSO-d6, internal standard substance: TMS): δ 3.14 (6H), δ 3.34 (6H), δ4.55 (3H), δ 7.48 (3H), δ 7.60 (2H).

Example 6 Preparation of a Compound Represented by the Compound No. 3-45in Table 3-1

11.15 g (0.105 mole) of 3-mercaptothietane was introduced to 50 g ofpure water. Subsequently, 41.2 g (0.103 mole) of a 10% NaOH aqueoussolution was introduced dropwise at room temperature over 40 minutes.Then, the reaction solution was subjected to a temperature elevation to30° C. and 109.8 g (corresponding to 0.050 mole of methyl tindichloride) of an aqueous solution of 10% methyl tin dichloride wasinserted dropwise at the same temperature over 4 hours. After thedropwise addition was completed, the solution was further stirred at thesame temperature for 2 hours. 100 ml of chloroform was added to thereaction mixture, and the organic layer and the water layer wereseparated. The organic layer was washed with 100 ml of pure water twice,and then dried over anhydrous sodium sulfate. The solvent was distilledoff from the extract to obtain 17.42 g (Yield: 97%) of a compoundrepresented by the Compound No. 3-45 in Table 3-1. ¹H-NMR data are shownin the following (solvent: CDCl₃, internal standard substance: TMS): δ0.78 (6H), δ 3.24 (4H), δ 3.44 (4H), δ 4.55 (2H).

Example 7 Preparation of a Compound Represented by the Compound No. 3-75in Table 3-2

5.42 g (0.051 mole) of 3-mercaptothietane and 4.01 g (0.026 mole) ofmercaptoethyl sulfide were introduced to 50 g of pure water.Subsequently, 41.2 g (0.10 mole) of a 10% NaOH aqueous solution wasintroduced dropwise at room temperature over 40 minutes. Then, thereaction solution was subjected to a temperature elevation to 30° C. and65.2 g (corresponding to 0.025 mole of tin tetrachloride) of an aqueoussolution of 10% tin tetrachloride was inserted dropwise at the sametemperature over 4 hours. After the dropwise addition was completed, thesolution was further stirred at the same temperature for 2 hours. 100 mlof chloroform was added to the reaction mixture, and the organic layerand the water layer were separated. The organic layer was washed with100 ml of pure water twice, and then dried over anhydrous sodiumsulfate. The solvent was distilled off from the extract to obtain acoarse composition. The resulting coarse composition was purified bysilica gel column chromatography with a development solvent ofchloroform to obtain 8.42 g (Yield: 70%) of a compound represented bythe Compound No. 3-75 in Table 3-2. ¹H-NMR data are shown in thefollowing (solvent: CDCl₃, internal standard substance: TMS): δ 2.91(4H), δ 3.11 (4H), δ 3.28˜3.56 (8H), δ 4.79 (2H).

Example 8 Preparation of a Compound Represented by the Compound No. 3-2in Table 3-1

7.71 g (Yield: 65%) of a compound represented by the Compound No. 3-2 inTable 3-1 was obtained by carrying out the same operation as in Example1, except that 3-thiethanol was used instead of 3-mercaptothietane.¹H-NMR data are shown in the following (solvent: DMSO-d6, internalstandard substance: TMS): δ 3.22 (16H), δ 4.96 (4H).

Example 9 Preparation of a Compound Represented by the Compound No.3-245 in Table 3-5

11.15 g (0.105 mole) of 3-mercaptothietane was introduced to 50 g ofpure water. Subsequently, 41.2 g (0.103 mole) of a 10% NaOH aqueoussolution was introduced dropwise at room temperature over 40 minutes.Then, 68.2 g (corresponding to 0.050 mole of zinc chloride) of anaqueous solution of 10% zinc chloride was inserted dropwise at the sametemperature over 4 hours. After the dropwise addition was completed, thereaction solution was further stirred at the same temperature for 2hours. The resultant product was filtered off, washed with 30 ml ofmethanol twice, and vacuum-dried at room temperature to obtain 13.13 g(Yield: 95%) of a compound represented by the Compound No. 3-245 inTable 3-5. ¹H-NMR data are shown in the following (solvent: DMSO-d6,internal standard substance: TMS): δ 3.22 (8H), δ 4.50 (2H).

Example 10 Preparation of a Compound Represented by the Compound No.3-141 in Table 3-3

10.62 g (0.100 mole) of 3-mercaptothietane was introduced to 65 g ofdried hexane, and 10.12 g (0.100 mole) of triethylamine dried at 20° C.to 25° C. was added thereto at the same temperature and stirred for 5minutes. A solution of 4.25 g (0.025 mole) of silicon tetrachloridedissolved in 18 g of hexane was added dropwise at 20° C. to 25° C. tothe obtained mixture over 40 minutes. After the dropwise addition wascompleted, the reaction solution was further stirred at the sametemperature for 6 hours. The resultant product precipitated along withthe by-product triethylamine hydrochloride was filtered off. The coarsecomposition was washed successively with 50 ml of pure water and 50 mlof methanol twice respectively, and vacuum-dried at room temperature toobtain 7.86 g (Yield: 70%) of a compound represented by the Compound No.3-141 in Table 3-3. ¹H-NMR data are shown in the following (solvent:CDCl₃, internal standard substance: TMS): δ 3.24 (8H), δ 3.55 (8H), δ4.65 (4H).

Example 11

[Preparation of a Compound Represented by the Compound No. 3-142 inTable 3-3]

7.21 g (Yield: 75%) of a compound represented by the Compound No. 3-142in Table 3-3 was obtained by carrying out the same operation as inExample 10, except that 3-thiethanol was used instead of3-mercaptothietane. ¹H-NMR data are shown in the following (solvent:DMSO-d6, internal standard substance: TMS): δ 3.03 (8H), δ 3.30 (8H), δ4.89 (4H).

Example 12 Preparation of a Compound Represented by the Compound No.3-193 in Table 3-4

8.74 g (Yield: 71%) of a compound represented by the Compound No. 3-193in Table 3-4 was obtained by carrying out the same operation as inExample 10, except that germanium tetrachloride was used instead ofsilicon tetrachloride. ¹H-NMR data are shown in the following (solvent:CDCl₃, internal standard substance: TMS): δ 3.26 (8H), δ 3.55 (8H), δ4.68 (4H).

Example 13 Preparation of a Compound Represented by the Compound No.3-179 in Table 3-4

6.37 g (0.060 mole) of 3-mercaptothietane was introduced to 50 g ofdried hexane, and 6.07 g (0.060 mole) of triethylamine dried at 20° C.to 25° C. was added thereto at the same temperature and stirred for 5minutes. A solution of 4.23 g (0.020 mole) of phenyl trichlorosilanedissolved in 18 g of hexane was added dropwise at 20° C. to 25° C. tothe obtained mixture over 40 minutes. After the dropwise addition wascompleted, the reaction solution was further stirred at the sametemperature for 6 hours. 100 g of hexane was put to the reaction mixtureand the by-product triethylamine hydrochloride was precipitated. Thetriethylamine hydrochloride was filtered off to obtain a filtrate, andthe solvent was distilled off from the obtained filtrate to obtain 2.52g (Yield: 30%) of a compound represented by the Compound No. 3-179 inTable 3-4. ¹H-NMR data are shown in the following (solvent: CDCl₃,internal standard substance: TMS): δ 3.06 (6H), δ 3.52 (6H), δ 4.54(3H), δ 7.44 (3H), δ 7.68 (2H).

<Preparation of the Polymerizable Composition of the Present Inventionand Preparation of the Resin Cured Product by the Polymerization>

The physical properties of the resins or optical components (lenses)prepared in Examples were evaluated in the following methods.

-   -   Appearance: color, transparency, and optical strain were        confirmed visually or using a microscope.    -   Refractive index: It was measured at 20° C. using a Pulfrich        refractometer.

Example 14

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-1 in Table 3-1 prepared in Example 2 was weighed in aglass beaker, filtered off using a PTFE filter without adding apolymerization catalyst, and then thoroughly degassed under a reducedpressure of not more than 1.3 kPa until no bubble was observed. Thepolymerizable composition was filled into a mold composed of a glassmold and a tape. Then, the resultant was put into a heating oven,subjected to a temperature elevation up to 30° C. to 120° C. slowly, andpolymerized for 20 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.790.

Example 15

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-35 in Table 3-1 prepared in Example 3 was weighed in aglass beaker, and as a polymerization catalyst, 0.15 g of amercaptopropionic acid was added thereto, and then the resulting mixturewas stirred for fully mixing. The obtained mixed solution was filteredoff using a PTFE filter, and then thoroughly degassed under a reducedpressure of not more than 1.3 kPa until no bubble was observed. Thepolymerizable composition was filled into a mold composed of a glassmold and a tape. Then, the resultant was put into a heating oven,subjected to a temperature elevation up to 80° C. to 120° C. slowly, andpolymerized for 30 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.755.

Example 16

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-41 in Table 3-1 prepared in Example 4 was weighed in aglass beaker, and as a polymerization catalyst, 0.15 g of atrifluoroacetic acid was added thereto, and then the resulting mixturewas stirred for fully mixing. The obtained mixed solution was filteredoff using a PTFE filter, and then thoroughly degassed under a reducedpressure of not more than 1.3 kPa until no bubble was observed. Thepolymerizable composition was filled into a mold composed of a glassmold and a tape. Then, the resultant was put into a heating oven,subjected to a temperature elevation up to 80° C. to 120° C. slowly, andpolymerized for 30 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.720.

Example 17

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-45 in Table 3-1 prepared in Example 6 was weighed in aglass beaker, and as a polymerization catalyst, 0.15 g of atrifluoroacetic acid and 0.15 g of a mercaptopropionic acid were addedthereto, and then the resulting mixture was stirred for fully mixing.The obtained mixed solution was filtered off using a PTFE filter, andthen thoroughly degassed under a reduced pressure of not more than 1.3kPa until no bubble was observed. The polymerizable composition wasfilled into a mold composed of a glass mold and a tape. Then, theresultant was put into a heating oven, subjected to a temperatureelevation up to 80° C. to 120° C. slowly, and polymerized for 80 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.711.

Example 18

At room temperature (25° C.), 24 g of the compound represented by theCompound No. 3-45 in Table 3-1 prepared in Example 6 and 6 g of thecompound represented by the Compound No. 3-1 in Table 3-1 prepared inExample 2 were weighed in a glass beaker, filtered off using a PTFEfilter without adding a polymerization catalyst, and then thoroughlydegassed under a reduced pressure of not more than 1.3 kPa until nobubble was observed. The polymerizable composition was filled into amold composed of a glass mold and a tape. Then, the resultant was putinto a heating oven, subjected to a temperature elevation up to 80° C.to 120° C. slowly, and polymerized for 60 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.729.

Example 19

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-75 in Table 3-2 prepared in Example 7 was weighed in aglass beaker, filtered off using a PTFE filter without adding apolymerization catalyst, and then thoroughly degassed under a reducedpressure of not more than 1.3 kPa until no bubble was observed. Thepolymerizable composition was filled into a mold composed of a glassmold and a tape. Then, the resultant was put into a heating oven,subjected to a temperature elevation up to 80° C. to 120° C. slowly, andpolymerized for 20 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.776.

Example 20

At room temperature (25° C.), 30 g of the compound represented by theCompound No. 3-2 in Table 3-1 prepared in Example 8 was weighed in aglass beaker, and as a polymerization catalyst, 0.15 g of atrifluoromethane sulfonic acid was added thereto, and then the resultingmixture was stirred for fully mixing. The obtained mixed solution wasfiltered off using a PTFE filter, and then thoroughly degassed under areduced pressure of not more than 1.3 kPa until no bubble was observed.The polymerizable composition was filled into a mold composed of a glassmold and a tape. Then, the resultant was put into a heating oven,subjected to a temperature elevation up to 30° C. to 120° C. slowly, andpolymerized for 20 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.760.

Example 21

At 30° C., 30 g of the compound represented by the Compound No. 3-141 inTable 3-3 prepared in Example 10 was weighed in a glass beaker, and as apolymerization catalyst, 0.15 g of a trifluoromethane sulfonic acid wasadded thereto, and then the resulting mixture was stirred for fullymixing. The obtained mixed solution was filtered off using a PTFEfilter, and then thoroughly degassed under a reduced pressure of notmore than 1.3 kPa until no bubble was observed. The polymerizablecomposition was filled into a mold composed of a glass mold and a tape.Then, the resultant was put into a heating oven, subjected to atemperature elevation up to 30° C. to 120° C. slowly, and polymerizedfor 20 hours. A sample piece of the obtained resin was excellent intransparency and had good appearance with no strain. The refractiveindex (nd) of the obtained resin was measured. As a result, it was1.754.

Example 22

At 40° C., 30 g of the compound represented by the Compound No. 3-193 inTable 3-4 prepared in Example 12 was weighed in a glass beaker, and as apolymerization catalyst, 0.30 g of a trifluoroacetic acid was addedthereto, and then the resulting mixture was stirred for fully mixing.The obtained mixed solution was filtered off using a PTFE filter, andthen thoroughly degassed under a reduced pressure of not more than 1.3kPa until no bubble was observed. The polymerizable composition wasfilled into a mold composed of a glass mold and a tape. Then, theresultant was put into a heating oven, subjected to a temperatureelevation up to 80° C. to 120° C. slowly, and polymerized for 70 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.752.

Example 23

At room temperature (25° C.), 24 g of the compound represented by theCompound No. 3-193 in Table 3-4 prepared in Example 12 and 6 g of thecompound represented by the Compound No. 3-1 in Table 3-1 prepared inExample 2 were weighed in a glass beaker, and as a polymerizationcatalyst, 0.30 g of a mercaptopropionic acid was added thereto, and thenthe resulting mixture was stirred for fully mixing. The obtained mixedsolution was filtered off using a PTFE filter, and then thoroughlydegassed under a reduced pressure of not more than 1.3 kPa until nobubble was observed. The polymerizable composition was filled into amold composed of a glass mold and a tape. Then, the resultant was putinto a heating oven, subjected to a temperature elevation up to 80° C.to 120° C. slowly, and polymerized for 70 hours.

A sample piece of the obtained resin was excellent in transparency andhad good appearance with no strain. The refractive index (nd) of theobtained resin was measured. As a result, it was 1.762.

The resin obtained by polymerization of the polymerizable compound ofthe present invention has high transparency, good heat resistance andmechanical strength, while attaining a high refractive index (nd)exceeding 1.7. Therefore, the resin of the present invention is usefulas a resin for use in optical components such as plastic lenses and thelike.

1. A compound represented by the general formula (3),

wherein, in the formula, M represents a metal atom; X_(i) and X₂ eachindependently represent a sulfur atom or an oxygen atom; R₁ represents adivalent organic group; m represents an integer of or 1 or more; prepresents an integer of from 2 to n; n represents a valence of a metalatom M; Yq each independently represent an inorganic or organic residue;and when (n−p) is 2 or more, Yq may be bonded to one another for forminga ring structure with the intermediary of a metal atom M.
 2. Thecompound according to claim 1, wherein the metal atom is a Sn atom, a Siatom, a Zr atom, a Ge atom, a Ti atom, a Zn atom, an Al atom, a Fe atom,a Cu atom, a Pt atom, a Pb atom, an Au atom or an Ag atom.
 3. Thecompound according to claim 1, wherein the metal atom is a Sn atom, a Siatom, a Zr atom, a Ti atom, a Ge atom, an Al atom, a Pb atom or a Znatom.
 4. A polymerizable composition comprising at least one compound asdescribed in claim
 1. 5. A polymerizable composition comprising at leastone compound as described in claim
 2. 6. A polymerizable compositioncomprising at least one compound as described in claim 3.